JP2010072212A - Sealant composition for liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a frame sealant for a liquid crystal display device which does not deteriorate the characteristics of a liquid crystal display device. <P>SOLUTION: A sealant composition for a liquid crystal display device includes particles, to which one or more kinds of photoinitiator molecules are adhered, and one or more kinds of polymerizable compounds. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a sealant composition for a liquid crystal display device that is cured by light, a liquid crystal display device manufactured using the sealant, and a method for manufacturing the same.

  In recent years, the liquid crystal display is the most widespread flat panel display from a small type for mobile use to a large type for television. This spread in the market is due to the widely recognized characteristics of liquid crystal displays that are not found in conventional displays, such as light weight, energy saving, space saving, and long life.

  As a manufacturing method of the liquid crystal display, there is a method of assembling a cell having a gap into which liquid crystal can be injected by bonding glass substrates each having a drive electrode and a color filter using an adhesive, and then injecting liquid crystal into the gap. It has been used.

  More recently, there has been proposed a dropping method in which a glass substrate in which a sealant is previously applied to a frame shape is prepared, a liquid crystal is dropped at the center, and then the glass substrate is attached to assemble a cell (Patent Document 1).

  The above dripping method is excellent in that the liquid crystal injection time can be greatly shortened and the liquid crystal can be used without waste. On the other hand, since the liquid crystal and the sealing agent are in contact with each other before curing or during the curing, the cell As compared with the conventional method in which liquid crystal is injected after assembling, there is a problem that the amount of impurities eluted from the sealant composition to the liquid crystal increases. Moreover, since it hardens | cures after bonding a glass panel, there also exists a problem which the outgas at the time of hardening fills in a cell, and degrades a display characteristic.

  In order to solve these problems, a large number of sealing agent compositions with little contamination to liquid crystals have been disclosed (Patent Documents 2 and 3).

  Moreover, in order to suppress the elution of the pollutant at the time of thermosetting, the sealing agent composition of the type cured with light (Patent Document 4) or the two-stage curing type cured with light and then cured with heat (Patent Document 5) Many are also disclosed.

As another method for suppressing elution from the sealing agent composition, the polymerizable compound may have a polar group such as a hydroxyl group or an amino group to reduce the solubility in liquid crystals (Patent Document 6), or to the photoinitiator molecule. A method using a compound having a substituent that chemically reacts with a polymerizable compound is disclosed (Patent Document 7).
Japanese Patent Laid-Open No. 9-5759 JP-A-9-194567 JP 2005-308813 A JP2005-308812 International Publication Number WO2004 / 027502 International Publication Number WO2002 / 092718 JP 2001-133794 A

  The conventional heat-curing type sealant composition is heat-cured in the state of a liquid polymerizable compound, so that a large amount of outgas is generated, and more impurities are eluted when heated while touching the liquid crystal. .

  Here, the impurity is a component that dissolves in the liquid crystal from the sealing agent composition for liquid crystal display devices and a component that contaminates the alignment film, and decreases the orientation of the liquid crystal or changes the electrical characteristics of the liquid crystal cell. It mainly refers to components that degrade display characteristics. Examples of such deterioration components include ionic impurities, components having a dielectric constant different from that of liquid crystals, and substances that become deterioration components by causing a chemical change during a long-term durability test. In particular, low molecular weight compounds tend to cause deterioration in display characteristics due to their high elution properties. Applicable components include photoinitiators and their photolysis products. In addition, thermosetting agents, polymerizable compounds, coupling agents, and the like can be cited as degradation components, but they are relatively difficult to elute when incorporated into a polymer having a chemical bond with the polymerizable compound.

  In other words, the type that cures only with light does not require heating at the time of curing, so there is little outgas and elution of impurities is difficult to occur, but liquid crystals such as photoinitiators and decomposition products derived from photoinitiators are used when annealing liquid crystals. Contamination is likely to occur.

  The type that is cured by light and then thermally cured is liable to be contaminated with liquid crystal due to a photoinitiator or a thermosetting agent during the heat curing.

  The method of imparting a polar group to the polymerizable compound is also insufficient for suppressing the elution of photoinitiator and thermosetting agent molecules.

  Even when a type having a reactive substituent is used for the photoinitiator molecule, if a molecule that cannot be chemically bonded to the polymerizable compound molecule is generated, there is a high possibility of elution to the liquid crystal, which is not effective from the viewpoint of suppressing elution. It is enough.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that the photoinitiator molecules have been separated from the surface of the particles so that photoinitiators and photoinitiator decomposition products that are likely to be eluted into the liquid crystal are not eluted into the liquid crystal. As a result, the photoinitiator and the photoinitiator decomposition product are reliably kept in the resin composition, and the present invention has been completed by finding out a method in which these components do not elute into the liquid crystal during thermal curing or annealing.

Therefore, 1st this invention relates to the sealing compound composition for liquid crystal display devices characterized by including the particle | grains to which the 1 or more types of photoinitiator molecule was made to adhere, and 1 or more types of polymeric compounds. .
In addition, by using a clay layered compound as the particles, photocuring agent molecules can be easily attached using an intercalation method, and since the clay layered compound has a nano-level sheet structure, It has been found that the amount of can be increased, and the present invention has been completed.

  In addition, it has been found that by using metal nanoplates as the particles, it is possible to improve the curability of the wiring shadow due to light scattering, and by further aligning the metal nanoplate with a magnetic field and / or an electric field, the shadow is cured. It has been found that the properties can be further improved, and the third invention has been completed.

  In addition, it has been found that the adhesion of one or more kinds of thermosetting agent molecules to the surface of the particles can enhance the properties of the sealant and the interaction with the particles, and the fourth invention has been completed. I came to let you.

  In addition, it has been found that by further attaching the one or more kinds of polymerizable compound molecules to the surface of the particles, the properties of the sealant and the interaction with the particles can be strengthened. It came to complete.

  In addition, by using a particle that emits fluorescence and / or phosphorescence, or a composite particle to which fluorescence and / or phosphor molecules are attached as the particle, even through a material that does not transmit a wavelength effective for the photoinitiator during photocuring. It was found that it could be cured, and the sixth invention was completed.

  In addition, by using a particle having a particle diameter of 500 nm or less, it has been found that the specific surface area can be increased to increase the amount of attached molecules, and further, attenuation due to light scattering during photocuring can be prevented. As a result, the inventors have completed the seventh invention.

  Further, it has been found that a liquid crystal display device can be obtained using the above-mentioned sealing agent composition, and that the above-mentioned sealing agent composition can be preferably applied to a method for producing a liquid crystal display device, particularly a dripping method. The present invention has been completed.

(First invention)
Since the photoinitiator molecule adheres to the surface of the particles, the sealant composition of the first aspect of the present invention can prevent impurities derived from the photoinitiator from eluting into the liquid crystal.
Further, according to the first aspect of the present invention, any particle can be applied to any combination as long as the photoinitiator molecule adheres to such an extent that elution into the liquid crystal is reduced.
Further, a combination of a photoinitiator and a sensitizer, or two or more photoinitiators having different absorption wavelengths can be used in combination, and the ability as a photoinitiator can be enhanced. Furthermore, as such a combination, a tertiary amine and a hydrogen abstraction type photoinitiator can be exemplified. In this case, the interaction can be enhanced by reducing the intermolecular distance. Moreover, when applied to a photo radical initiator, the lifetime of radicals can be extended by hindering the coupling reaction between the generated radical species by the steric hindrance of the particles. As a result, the amount of photoinitiator added can be reduced. It is also possible to shift the absorption wavelength to the longer wavelength side by interaction with clay.
Furthermore, the photoinitiator reaction efficiency can be increased by adsorbing the photoinitiator molecules so that the transition moments are aligned in the direction in which the light absorption is maximized.
The above-mentioned photoinitiator and polymerizable compound can be applied to various types, and for example, can be preferably applied to the photocurable resin described in 1989 by Kiyomi Kato, “UV Curing System”, published by General Technology Center Co., Ltd. .

(Second invention)
According to 2nd this invention, adhesion of the photoinitiator molecule | numerator by intercalation can be performed by using a clay layered compound as said particle | grains. Such attachment can be easily carried out by exchange reaction with a cation between clay layers if a photoinitiator molecule having an amino group is used.
Furthermore, after replacing the clay layer with a molecule having a reactive substituent, the photoinitiator molecule is bonded by a chemical bond, or it is attached by a hydrophobic-hydrophobic interaction by replacing with a molecule having hydrophobicity. You can also. Since the clay layered compound has a plate-like structure with high anisotropy, the mechanical properties of the sealant can be improved and the gas barrier property can be improved.

(Third invention)
According to the third aspect of the present invention, since the metal nanoplate is used as the particles, the back of the wiring can be photocured by utilizing the light reflection of the metal nanoplate. Metal nanoplates can also be oriented in an advantageous direction for reflection using electric and / or magnetic fields due to anisotropy of the molecules attached to the surface and induced current.

(Fourth and fifth inventions)
According to the fourth and fifth aspects of the present invention, one or more types of thermosetting agent molecules and / or one or more types of polymerizable compound molecules are attached to the particles, thereby improving the characteristics of the resin matrix. , Can improve the reactivity. In particular, by combining photoinitiator molecules and thermosetting agent molecules and attaching them to a single particle, the particles, resin, photoinitiator molecules, and thermosetting agent molecules can be integrated, so impurities in the liquid crystal In addition to the effect of suppressing elution, it is possible to enhance properties such as adhesion, moisture resistance, and mechanical strength required for the sealant. As such thermosetting agent molecules, those capable of thermally polymerizing a polymerizable compound can be appropriately selected. Examples of such a polymerizable compound molecule include a combination of a molecule having a thermosetting epoxy group and a molecule having a photocurable acrylic group, and a combination of a molecule having an acrylic group and a molecule having a methacryl group. The reactivity can be enhanced by the presence of photoinitiator molecules and thermosetting agent molecules that can be polymerized in the vicinity of these molecules on the surface of one particle.

(Sixth present invention)
According to the sixth aspect of the present invention, by using particles that generate fluorescence and / or phosphorescence, or by using composite particles in which molecules of substances that generate fluorescence and / or phosphorescence are attached to the particle surface, for example, Photocuring is possible even under conditions where the photoinitiator is active in the ultraviolet region and does not pass ultraviolet light. Here, examples of conditions where ultraviolet rays do not pass can include the case of irradiating ultraviolet rays through a color filter and the case of attaching a filter that cuts a low wavelength component to an ultraviolet irradiation device in order to reduce damage to the panel.

(Seventh Invention)
According to the seventh aspect of the present invention, the amount of photoinitiator molecules attached can be increased by making the particles 500 nm or less. Furthermore, since the nanoparticle has a large specific surface area, the interaction with the resin can be strengthened, so that the physical properties of the sealing agent can be enhanced.

  The sealant composition in the present invention is characterized by containing particles in which one or more kinds of photoinitiator molecules are attached to the surface of the particles. As will be described later, thermosetting agent molecules and polymerizable compound molecules can be attached to the particles as necessary.

  The particles in the present invention are not limited to types and shapes as long as they can attach molecules to the surface, and any particles can be used. Examples of the particles include particles of metal oxides such as alumina, silica, zirconia, titania, zinc oxide, tin oxide, and indium oxide; sols such as colloidal silica, titania sol, and alumina sol; hydrotalcite group compounds, serpentine-kaolin Group compounds, talc pyrophyllite group compounds, smectite group compounds, vermiculite group compounds, mica groups, interlaminar defect type mica compounds, brittle mica group compounds, chlorite group compounds, mixed layer minerals, diatomaceous earth, aluminum silicate, etc. Particles of clay minerals; particles of carbides such as silicon carbide and titanium carbide; particles of carbonates such as ammonium carbonate, sodium bicarbonate, barium carbonate, strontium carbonate, manganese carbonate, calcium carbonate; silicon nitride, aluminum nitride, titanium nitride Nitride particles such as boron nitride and boron Boride particles such as titanium and boron oxide; composite oxide particles such as mullite and barium titanate; hydroxide particles such as aluminum hydroxide and magnesium hydroxide; Ag, Cu, Au, Al, Mg, Rh , W, Mo, Co, Ni, Pt, Pd, Cr, Ta, Pb, V, Zr, Ti, In, Fe, Zn, or other metal particles or nanoplates; Sn—Pb, Sn—In, Sn -Particles of alloys such as Bi-based, Sn-Ag-based, Sn-Zn-based alloys; carbon racks such as acetylene black, furnace black, channel black, graphite, graphite fiber, graphite fibril, carbon fiber, activated carbon, charcoal, carbon nanotube Particles of carbon-based materials such as polypropylene, polyethylene and polyethylene Polymer particles such as ester, polyvinyl alcohol, polyvinylidene fluoride, cellulose, polyamide, polyimide, nylon, acrylic resin, epoxy resin, polybutadiene, silicone; solid organic particles such as amine adduct; anthracene, p-nitroaniline, urea And particles of crystalline organic substances such as lysotium; semiconductor particles such as silicon, gallium, zinc selenide, and gallium arsenide. Such particles can be used alone or in combination of two or more.

  As the particles, a clay layered compound is preferable, and by using this, a photocuring agent molecule and / or a thermosetting agent molecule can be easily attached using an intercalation method. Because of the sheet structure, the amount of molecules to be attached can be increased. Such attachment can be easily performed by exchange reaction with a cation between clay layers if a photoinitiator or thermosetting agent molecule having an amino group is used. Furthermore, after the clay layer is replaced with molecules having reactive substituents, the photoinitiator and thermosetting agent molecules are bonded by chemical bonds, or the hydrophobic layers are replaced by hydrophobic molecules. Can also be attached. Since the clay layered compound has a plate-like structure with high anisotropy, the mechanical properties of the sealant can be improved and the gas barrier property can be improved.

  A metal nanoplate is preferable as the particle, and light curing can be performed to the back of the wiring by utilizing the light reflection of the metal nanoplate. Metal nanoplates can also be oriented in an advantageous direction for reflection using electric and / or magnetic fields due to anisotropy of the molecules attached to the surface and induced current.

  In addition to the above-mentioned particles made of a single material, composite particles can be used. Examples of the composite particles include metal / molecular core / shell type particles, polymer / metal core / shell type particles, and polymer particles in which inorganic fine particles are kneaded.

As the particles, particles that emit fluorescence and / or phosphorescence, or composite particles to which fluorescence and / or phosphor molecules are attached can be used. For example, photoinitiators of the type that become active in the ultraviolet region can be used. On the other hand, photocuring is possible even under conditions where ultraviolet rays do not pass. Here, examples of conditions where ultraviolet rays do not pass can include the case of irradiating ultraviolet rays through a color filter and the case of attaching a filter that cuts a low wavelength component to an ultraviolet irradiation device in order to reduce damage to the panel.
Examples of the particles that emit fluorescence and / or phosphorescence include lithium fluoride, calcium fluoride, zinc sulfide, strontium aluminate, and calcium aluminate.

Examples of composite particles to which fluorescent and / or phosphor molecules are attached include, for example,
N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidine,
N, N′-bis (naphthalen-2-yl) -N, N′-bis (phenyl) -benzidine,
N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -benzidine,
N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-spirobifluorene,
N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -9,9-spirobifluorene,
N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-dimethyl-fluorene,
N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -9,9-dimethyl-fluorene,
N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-diphenyl-fluorene,
N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -9,9-diphenyl-fluorene,
2,2 ′, 7,7′-tetrakis (N, N-diphenylamino) -9,9′-spirobifluorene,
9,9-bis [4- (N, N-bis-biphenyl-4-yl-amino) phenyl] -9H-fluorene,
9,9-bis [4- (N, N-bis-naphthalen-2-yl-amino) phenyl] -9H-fluorene,
9,9-bis [4- (N, N′-bis-naphthalen-2-yl-N, N′-bis-phenyl-amino) -phenyl] -9H-fluorene,
2,2 ′, 7,7′-tetrakis [N-naphthalenyl (phenyl) -amino] -9,9-spirobifluorene,
N, N′-bis (phenanthren-9-yl) -N, N′-bis (phenyl) -benzidine,
2,7-bis [N, N-bis (9,9-spiro-bifluoren-2-yl) -amino] -9,9-spirobifluorene,
2,2′-bis [N, N-bis (biphenyl b-4-yl) amino] -9,9-spirobifluorene,
2,2′-bis (N, N-di-phenyl-amino) -9,9-spirobifluorene,
Di- [4- (N, N-ditolyl-amino) -phenyl] cyclohexane,
2,2 ′, 7,7′-tetra (N, N-di-tolyl) amino-spiro-bifluorene,
N, N, N ′, N′-tetra-naphthalen-2-yl-benzidine,
Phthalocyanine / copper composite,
Titanium oxide phthalocyanine,
2,3,5,6-tetrafluoro-7,7,8,8, -tetracyano-quinodimethane q,
Pyrazino [2,3-f] [1,10] phenanthroline-2,3-dicarbonitrile,
N, N, N ′, N′tetrakis (4-methoxyphenyl) benzidine,
2,7-bis [N, N-bis (4-methoxy-phenyl) amino] -9,9-spirobifluorene,
2,2′-bis [N, N-bis (4-methoxy-phenyl) amino] -9,9-spirobifluorene,
N, N′-di-phenyl-N, N′-di- [4- (N, N-di-tolyl-amino) phenyl] benzidine,
N, N′-di-phenyl-N, N′-di- [4- (N, N-di-phenyl-amino) phenyl] benzidine,
N, N′-di (naphthalen-2-yl) -N, N′-diphenylbenzene-1,4-diamine,
8-hydroxyquinolinolato-lithium,
2,2 ′, 2 ″-(1,3,5-benzidinetriyl) -tris (1-phenyl-1-H-benzimidazole),
2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole,
2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline,
4,7-diphenyl-1,10-phenanthroline,
Bis (2-methyl-8-quinolinolato) -4- (phenylphenolato) aluminum,
1,3-bis [2- (2,2′-bipyridin-6-yl) -1,3,4-oxadiazo-5-yl] benzene,
6,6′-bis [5- (biphenyl-4-yl) -1,3,4-oxadiazo-2-yl] -2,2′-bipyridyl,
3- (4-biphenylyl) -4-phenyl-5-tert-butylphenyl-1,2,4-triazole,
4- (naphthalen-1-yl) -3,5-diphenyl-4H-1,2,4-triazole,
2,9-bis (naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline,
2,7-bis [2- (2,2′-bipyridin-6-yl) -1,3,4-oxadiazo-5-yl] -9,9-dimethylfluorene,
1,3-bis [2- (4-tert-butylphenyl) -1,3,4-oxadiazo-5-yl] benzene,
Tris (2,4,6-trimethyl-3- (pyridin-3-yl) phenyl) borane,
1-methyl-2- (4- (naphthalen-2-yl) phenyl) -1H-imidazo [4,5-f] [1,10] phenanthroline,
2- (naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline,
Tris (8-hydroxy-quinolinato) aluminum,
9,10-di (naphth-2-yl) anthracene,
3-Tert-butyl-9,10-di (naphth-2-yl) anthracene,
2,7-bis [9,9-di (4-methylphenyl) -fluoren-2-yl] -9,9-di (4-methylphenyl) fluorene,
2-methyl-9,10-bis (naphthalen-2-yl) anthracene,
2- (9,9′-spirobifluoren-2-yl) -9,9′-spirobifluorene,
2,7-bis (9,9′-spirobifluoren-2-yl) -9,9′-spirobifluorene,
2- [9,9-di (4-methylphenyl) -fluoren-2-yl] -9,9-di (4-methylphenyl) fluorene,
2,2′-di-pyrenyl-9,9-spirobifluorene,
1,3,5-tri (pyren-1-yl) benzene,
9,9-bis [4- (pyrenyl) phenyl] fluorene,
2,2′-bi (9,10-diphenyl-anthracene),
2,7-di-pyrenyl-9,9-spirobifluorene,
1,4-di (pyren-1-yl) benzene,
1,3-di (pyren-1-yl) benzene, 6,13-di-biphenyl-4-yl-pentacene,
A mixture of 3,9-di (naphthalen-2-yl) perylene and 3,10-di (naphthalen-2-yl) perylene,
1,3-bis (carbazol-9-yl) benzene,
1,3,5-tris (carbazol-9-yl) benzene,
4,4 ′, 4 ″ -tris (carbazol-9-yl) triphenylamine,
4,4′-bis (carbazol-9-yl) biphenyl,
4,4′-bis (9-carbazolyl) -2,2′-dimethylbiphenyl,
2,7-bis (carbazol-9-yl) -9,9-dimethylfluorene,
2,2 ′, 7,7′-tetrakis (carbazol-9-yl) -9,9′-spirobifluorene,
2,7-bis (carbazol-9-yl) -9,9-ditolylfluorene,
9,9-bis [4- (carbazol-9-yl) -phenyl] fluorene,
2,7-bis (9-carbazolyl) -9,9-spirobifluorene,
1,4-bis (triphenylsilyl) benzene,
1,3-bis (triphenylsilyl) benzene,
Bis (4-N, N-diethylamino-2-methylphenyl) -4-methylphenylmethane,
2,7-bis (9-carbazolyl) -9,9-dioctylfluorene,
Tris (phenylpyrazole) iridium,
3- (2-benzothiazolyl) -7- (diethylamino) coumarin,
2,3,6,7-tetrahydro-1,1,7,7, -tetramethyl-1H, 5H, 11H-10- (2-benzothiazolyl) quinolidino- [9,9a, 1gh] coumarin,
N, N′-dimethyl-quinacridone,
Tris (2-phenylpyridine) iridium (III),
Bis (2-phenylpyridine) (acetylacetonato) iridium (III),
Tris [2- (p-tolyl) pyridine] iridium (III),
9,10-bis [N, N-di- (p-tolyl) -amino] anthracene,
9,10-bis [phenyl (m-tolyl) -amino] anthracene,
Bis [2- (2-hydroxyphenyl) benzthiazolate] zinc (II),
4,4′-bis (9-ethyl-3-carbazovinylene) -1,1′-biphenyl,
Perylene,
2,5,8,11-tetra-tert-butylperylene,
1,4-bis [2- (3-N-ethylcarbazolyl) vinyl] benzene,
4,4′-bis [4- (di-p-tolylamino) styryl] biphenyl,
4- (di-p-tolylamino) -4 ′-[(di-p-tolylamino) styryl] stilbene,
Bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III),
4,4′-bis [4- (diphenylamino) styryl] biphenyl,
Bis (2,4-difluorophenylpyridinato) tetrakis (1-pyrazolyl) borate iridium (III),
N, N′-bis (naphthalen-2-yl) -N, N′-bis (phenyl) -tris- (9,9-dimethylfluorenylene),
2,7-bis {2- [phenyl (m-tolyl) amino] -9,9-dimethyl-fluoren-7-yl} -9,9-dimethyl-fluorene,
N- (4-((E) -2- (6-((E) -4- (diphenylamino) styryl) naphthalen-2-yl) vinyl) phenyl) -N-phenylbenzenamine,
2,7-bis [4- (diphenylamino) styryl] -9,9-spirobifluorene,
6-methyl-2- (4- (9- (4- (6-methylbenzo [d] thiazol-2-yl) phenyl) anthracen-10-yl) phenyl) benzo [d] thiazole,
fac-iridium (III) tris (1-phenyl-3-methylbenzimidazoline-2-ylidene-C, C2 ′),
mer-iridium (III) tris (1-phenyl-3-methylbenzimidazoline-2-ylidene-C, C2 ′),
1-4-di- [4- (N, N-di-phenyl) amino] styryl-benzene,
(E) -2- (2- (4- (dimethylamino) styryl) -6-methyl-4H-pyran-4-ylidene) malononitrile,
4- (dicyanomethylene) -2-methyl-6julolidyl-9-enyl-4H-pyran,
4- (dicyanomethylene) -2-methyl-6- (1,1,7,7-tetramethyljulolidyl-9-enyl) -4H-pyran,
4- (dicyanomethylene) -2-tert-butyl-6- (1,1,7,7-tetramethyljulolidin-4-yl-vinyl) -4H-pyran,
Tris (dibenzoylmethane) phenanthroline europium (III),
(5,6,11,12) -tetraphenylnaphthacene,
Bis (2-benzo [b] thiophen-2-yl-pyridine) (acetylacetonato) iridium (III),
Tris (1-phenylisoquinoline) iridium (III),
Bis (1-phenylisoquinoline) (acetylacetonato) iridium (III),
Bis [1- (9,9-dimethyl-9H-fluoren-2-yl) -isoquinoline] (acetylacetonato) iridium (III),
Bis [3- (9,9-dimethyl-9H-fluoren-2-yl) -isoquinoline] (acetylacetonato) iridium (III),
Tris [4,4′-di-tert-butyl- (2,2 ′)-bipyridine] ruthenium (III) complex,
Tris (2-phenylquinoline) iridium (III),
Bis (2-phenylquinoline) (acetylacetonato) iridium (III),
2,8-di-tert-butyl-5,11-bis (4-tert-butylphenyl) -6,12-diphenyltetracene,
Bis (2-phenylbenzothiazolate) (acetylacetonato) iridium (III),
Pt-tetraphenyltetrabenzoporphyrin,
Fluorescent and / or phosphor molecules such as can be attached to the particles by chemical bonding and / or physical adsorption.

  The particles in the present invention preferably have a particle size of 500 nm or less, more preferably 100 nm or less, and particularly preferably 20 nm or less. By using a material with a particle size of 500 nm or less, the specific surface area can be increased, the amount of adhesion of the molecule can be increased, and the interaction with the resin can be strengthened, so that the physical properties of the sealing agent can be enhanced. Attenuation due to light scattering during photocuring can be prevented. In addition, for plate-like particles such as clay layered compounds, aluminum hydroxide, and magnesium hydroxide, even if the particle diameter is larger than 500 nm, the same effect is obtained because the specific surface area increases when the thickness is small. In particular, a clay layered compound can easily obtain a nano-level ultrathin plate by cleavage of a silicate sheet layer in water.

  As the photoinitiator molecule in the present invention, one or more kinds can be arbitrarily selected according to the polymerizable compound to be cured, and examples thereof include a photo radical initiator, a photo cation initiator, and a photo anion initiator.

As a photo radical initiator for polymerizing a compound having an acrylic group, methacrylic group, allyl group, vinyl group, maleimide group, etc., 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone , Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4- Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-1 -[4- ( Methylthio) phenyl] -2-morpholinopropa Benzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc .; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, Benzophenones such as hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2 , 4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dii Thioxanthone series such as propylthioxanthone; 1-phenyl-1,2-propanedione-2 (O-ethoxycarbonyl) oxime, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, 9,10 -Phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 "-diethylisophthalophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone , 1- [4- (3-mercaptopropylthio) phenyl] -2-methyl-2-morpholin-4-yl-propan-1-one, 1- [4- (10-mercaptodecanylthio) phenyl]- 2-Methyl-2-morpholin-4-yl-propan-1-one, 1- (4- {2- [2 -(2-Mercapto-ethoxy) ethoxy] ethylthio} phenyl) -2-methyl-2-morpholin-4-yl-propan-1-one, 1- [3- (mercaptopropylthio) phenyl] -2-dimethylamino 2-benzyl-propan-1-one, 1- [4- (3-mercaptopropylamino) phenyl] -2-dimethylamino-2-benzyl-propan-1-one, 1- [4- (3-mercapto -Propoxy) phenyl] -2-methyl-2-morpholin-4-yl-propan-1-one, bis (η5-2,4-cyclopentadien-1-yl) bis [2,6-difluoro-3- ( 1H-bilol-1-yl) phenyl] titanium, α-allylbenzoin, α-allylbenzoin aryl ether, 1.2-octanedione, 1-4- (phenyl) Nylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,3-bis (p-dimethylaminobenzylidene) acetone, and the like.

  Among the above photoradical initiators, intermolecular hydrogen abstraction type photoinitiators can be added with an electron donor (hydrogen donor) as an initiator, and an aliphatic amine having active hydrogen as an initiator. Aromatic amines can be used. Specifically, triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, etc. It can be illustrated.

  As photocation initiators for polymerizing compounds having epoxy groups, oxirane rings such as oxetane rings, vinyl ethers, cyclic acetals, etc., diphenyliodonium, hexafluorophosphate, diphenyliodonium, hexafluoroantimonate, diphenyliodonium, tetrafluoroborate, diphenyl Iodonium, tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium, hexafluorophosphate, bis (dodecylphenyl) iodonium, hexafluoroantimonate, bis (dodecylphenyl) iodonium, tetrafluoroborate, bis (dodecylphenyl) iodonium , Tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methyl) Til) phenyliodonium, hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium, hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium, tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium, tetrakis (pentafluorophenyl) borate, 4-methoxydiphenyliodonium hexafluorophosphate, bis (4-methylphenyl) iodonium hexafluorophosphate, bis (4-tertiary -Butylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium, tricumyliodonium hexafluorophosphate, iodonium, Any iodonium salt; sulfonium salt such as triallylsulfonium hexafluoroantimonate; phosphonium salt such as triphenylpyrenylmethylphosphonium salt; (η6-benzene) (η5-cyclopentadienyl) iron (II) hexafluoroantimonate; Examples thereof include a combination of o-nitrobenzylsilyl ether and aluminum acetylacetonate.

  A sensitizer can be added to the photocationic initiator, and as such a sensitizer, 9,10-butoxyanthracene, acridine orange, acridine yellow, benzoflavin, cetoflavin T, perylene, pyrene, anthracene, phenothiazine, Examples include 1,2-benzacetracene, coronene, thioxanthone, fluorenone, benzophenone, anthraquinone and the like.

  As a photoanion initiator for polymerizing a compound having an epoxy group, a cyanoacrylate group, or the like, a 2-nitrobenzyl carbamate compound, a quinonediazide sulfonate ester compound and an N-blocked bifunctional or higher isocyanate blocked with an o-nitrobenzyl alcohol compound -A combination with an alkylaziridine compound can be exemplified.

Two or more of the above photoinitiators can be used in combination.
The polymerizable compound in the present invention is selected from compounds having epoxy, oxetane, spiroorthocarbonate, episulfide, vinyl ether, (meth) acrylic, vinylcaprolactam, maleimide, polyene (photopolymerization in combination with polythiol) as a reactive substituent. be able to.

  Examples of the compound having an epoxy group include (3 ′, 4′-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate, 4-vinylcyclohexene oxide, 1-methyl-4- (2-methyloxiranyl) -7. -Oxabicyclo [4.1.0] heptane, epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified epsilon-caprolactone, epoxidized polybutadiene, 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct, 1,2-epoxy-4- (2-oxiranyl) cyclosoxane adduct of 2,2-bis (hydroxymethyl) -1-butanol, 3 4-epoxycyclohexenylmethyl-3, '4'-epoxy Cyclohexene carboxylate, 3,4-epoxycyclohexylmethyl methacrylate, α-olefin epoxide, epoxidized product of styrene-butadiene block copolymer, epoxidized product of styrene-butadiene block copolymer, bisphenol A type epoxy resin, bisphenol AD type Epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, α-naphthol novolak type epoxy resin, bisphenol A novolac type epoxy resin, tetrabromobisphenol A type epoxy resin, Tetraglycidyldiaminodiphenylmethane, dihydroxynaphthalene / diglycidyl ether, biphenyl type epoxy resin, silce Kixane type epoxy resin, isoprene type epoxy resin, isobonyl skeleton, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, epoxy modified silicone, epoxy modified silsesquioxy An example is Sun.

  As the episulfide, an epoxy resin in which the oxygen atom of the above-described epoxy resin is substituted with a sulfur atom can be used.

  Examples of the compound having an oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [ 1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) Ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylme ) Ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, Dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxy Ethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2 Hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl) -3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa -Nonane, 3,3 '-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) ) Methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanyl) Methoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl- 3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl- 3-oxetanylmethoxy) hexane, Ntaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexas (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol Hexas (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrime Roll propane tetrakis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3-ethyl-3) -Oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3 -Ethyl-3-oxetanylmethyl) ether, oxetanylsilsesquioxane and the like can be exemplified.

  Examples of the compound having spiro ortho carbonate include spiro glycol diallyl ether and bicycloorthoester.

  The compounds having episulfide include ethylene sulfide, propylene sulfide, 1-butene sulfide, 2-butene sulfide, isobutylene sulfide, 1-pentene sulfide, 2-pentene sulfide, 1-hexene sulfide, 1-octene sulfide, 1-dode. Decene sulfide, cyclopentene sulfide, cyclohexene sulfide, styrene sulfide, vinylcyclohexene sulfide, 3-phenylpropylene sulfide, 3,3,3-trifluoropropylene sulfide, 3-naphthylpropylene sulfide, 3-phenoxypropylene sulfide, 3- Examples thereof include naphthoxypropylene sulfide, butadiene monosulfide, and 3-trimethylsilyloxypropylene sulfide.

  Examples of the compound having vinyl ether include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, allyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether. 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethano Distearate ether, triethylene glycol divinyl ether, trimethyl propane trivinyl ether, pentaerythritol tetravinyl ether, etc. can be exemplified.

  As the compound having a (meth) acryl group, butanediol mono (meth) acrylate, t-butylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) Acrylate, 2-ethoxyethyl (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxypropyl (meth) acrylate 2-methoxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, pyriethylene glycol 400 di (meth) acrylate, propylene glycol mono (meth) acrylate, polyethylene glycol Cole mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, vinyl acetate, (meth) acryloxyethyl phthalate, N- (meth) acryloxy-N-carboxypiperidine, N- (meth) acryloxy-N, N- Dicarboxymethyl-p-phenylenediamine, hydroxynaphthoxypropyl (meth) acrylate, (meth) acryloxyethyl phosphorisphenyl, 4- (meth) acryloxyethyl trimellitic acid, (meth) acryloxyethyl phthalate, (meth ) Acryloxyethyl phosphate, long chain aliphatic (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butanediol mono (meth) acrylate, butoxytrie Lenglycol (meth) acrylate, ECH-modified butyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, caprolactone (meth) acrylate, 3-chloro-2-hydroxypromyl (meth) acrylate, 2-cyanoethyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, alicyclic modified neopentyl glycol (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di Cyclopentenyloxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2-eth Xyloxy) ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, caprolactone modified 2- Hydroxyethyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyltrimethylammonium chloride, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, Lauryl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethyleneglycol (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol 1000 (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate , Morpholine (meth) acrylate, nonylphenoxypriethylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, octyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meta ) Acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexa Ethylene glycol (meth) acrylate, EO (EO = ethylene oxide) modified phenoxylated phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, EO modified phosphoric acid (meth) acrylate, EO modified phosphoric acid (meth) acrylate, EO modified Phthalic acid (meth) acrylate, EO, PO (PO = propylene oxide) modified phthalic acid (meth) acrylate, polyethylene glycol 90 (meth) acrylate, polyethylene glycol 200 (meth) acrylate, polyethylene glycol 400 (meth) acrylate, polypropylene glycol (Meth) acrylate, polypropylene glycol 500 (meth) acrylate, polypropylene glycol 800 (meth) acrylate, polyethylene glycol / polypropylene Glycol (meth) acrylate, stearyl (meth) acrylate, EO modified succinic acid (meth) acrylate, sulfonic acid soda ethoxy (meth) acrylate, tetrafluoropropyl (meth) acrylate, tetrahydrofurfuryl (meth) EO modified bisphenol A di ( (Meth) acrylate, acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, trifluoroethyl (meth) acrylate, vinyl acetate, allylcacyclohexyl di (meth) acrylate, (meth) acrylated isocyanurate, bis (acryloxyneopentyl) Glycol) adipate, EO modified bisphenol A di (meth) acrylate, EO modified bisphenol S di (meth) acrylate, bisphenol F di (meth) acrylate EO-modified bisphenol AD di (meth) acrylate, EO-modified bisphenol AF di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,3- Butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, diethylene glycol di (meth) acrylate, ECH Modified diethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, silsesquioxane (meth) acrylate, alkyl-modified dipenta Lithritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene glycol di (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, 1 , 6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol diacrylate, caprolactone modified hydroxypivalate neo Pentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (me ) Acrylate, stearic acid modified pentaerythritol di (meth) acrylate, EO modified phosphoric acid di (meth) acrylate, EO modified phosphoric acid tri (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, tetraethylene glycol di (meth) Acrylate, tetrabromobisphenol A di (meth) acrylate, triethylene glycol (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, cap Lactone-modified tris (acryloyloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, zinc di (meth) acrylate, isocyanatoethyl methacrylate, chlorendic di (meth) acrylate, and the like methoxy ether (meth) acrylate can be exemplified.

  A compound having a (meth) acrylic group can also be synthesized from the above-described epoxy resin. For example, (meth) acrylic acid (for example, a compound of the following formula (1)) and glycidyl ether (for example, of the following formula (2)) A compound having a (meth) acryl group (for example, a compound of the following formula (3)) can be obtained by the reaction of (compound) (formula 1).

（Ｒ^１は、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、炭素数７〜１８の芳香族環を有する基、上述の重合性置換基などを示す。）

(R ¹ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a group having an aromatic ring having 7 to 18 carbon atoms, the above-described polymerizable substituent, etc.)

  In this case, a composition with an arbitrary epoxy: acrylic group ratio can be obtained by changing the amount of acrylic acid and / or methacrylic acid charged to the epoxy group, and all of the epoxy resin in one molecule is epoxy (meth) acrylate. A compound comprising at least one epoxy (meth) acrylate and one epoxy group in each molecule, a composition comprising an epoxy resin not substituted with an acrylic group, and a composition comprising an epoxy resin can be obtained. The composition of arbitrary ratio can be obtained with the addition ratio with respect to the epoxy group of (meth) acrylic acid, reaction conditions, etc. In this case, acrylic acid and methacrylic acid can be added simultaneously to produce a compound having an acrylic group and a methacrylic group in one molecule.

  The compound having a (meth) acryl group can also be synthesized as a urethane acrylate having an epoxy group by reacting an epoxy resin having a hydroxyl group with a compound having an isocyanate group and a (meth) acryl group.

  Acrylic and / or methacrylated as described above can also be performed on a mixture of two or more epoxy resins. For example, a (meth) acrylated resin of high viscosity epoxy resin that has high viscosity and is difficult to synthesize is relatively It can be synthesized without using a solvent by diluting and mixing with an epoxy resin having a low viscosity and (meth) acrylating this mixture.

  For the polymerization of the above-described compound having an epoxy group and an acrylic and / or methacrylic group in one molecule, a photoinitiator and / or a thermosetting agent for curing the compound having an epoxy group, and an acrylic and / or methacrylic group are used. The photoinitiator and / or thermosetting agent which polymerize the compound which has can be used.

  Thus, it is possible to use a compound having two or more reactive substituents in one molecule, and it can be applied to combinations other than the above-mentioned combination of epoxy and acrylic.

  Examples of the compound having vinyl caprolactam include N-vinylcaprolactam and N-vinylpyrrolidone.

  Examples of the compound having maleimide include 4,4-diphenylmethane bismaleimide, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, and 2,2′-bis- [4- (4-maleimidophenoxy) phenyl]. Examples include propane.

  As other polymerizable compounds, 6,6′-sulfonylbis [3,4-dihydro-3-phenyl-2H-1,3-benzoxazine], 3,3 ′-(methylenedi) which self-polymerizes by heating. Examples include oxazine compounds such as -4,1-phenylene) bis [3,4-dihydro-2H-1,3-benzoxazine], and combinations of polyene and polythiol that cause photopolymerization.

  As the thermal curing agent in the present invention, a thermal radical curing agent, a thermal cationic curing agent, a hydrazide curing agent, an acid anhydride curing agent, a polycarboxylic acid curing agent, an amine adduct curing agent, an amine curing agent, and an imidazole A curing agent, an imidazoline-based curing agent, a phenol-based curing agent, or the like can be appropriately selected.

  Azides such as 4-azidoaniline hydrochloride and 4,4′-dithiobis (1-azidobenzene) as thermal radical curing agents for polymerizing compounds having acrylic, methacrylic, allyl, vinyl and maleimide groups Disulfides such as 4,4′-diethyl-1,2-dithiolane, tetramethylthiuram disulfide, tetraethylthiuram disulfide; octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic acid Peroxides, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as m-toluyl peroxide; di-n-propyl peroxydicarbonate, diisopropylperoxydicarbonate, Peroxydicarbonates such as 2-ethylhexylperoxydicarbonate, di- (2-ethoxyethyl) peroxydicarbonate; tertiary-butylperoxyisobutyrate, tertiary-butylperoxypivalate, tertiary-butylperoxyoctano Art, octylperoxyoctanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxyneododecanoate, octylperoxyneododecanoate, tert-butylperoxylaurate, tert-butyl Peroxyesters such as peroxybenzoate; di-tertiary-butyl peroxide, tertiary-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl Dialkyl peroxides such as 2,5- (tertiary-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tertiary-butyl) hexyne-3; 2,2-bis (tertiary-butylperoxy) butane 1,1-bis (tertiary-butylperoxy) cyclohexane, 1,1-bis (tertiary-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tertiary-butylperoxy) Peroxyketals such as valerate; ketone peroxides such as methyl ethyl ketone peroxide; peroxides such as p-menthane hydroperoxide, cumene hydroperoxide, cumene hydroperoxide, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutylnitrile), 1,1'-azobis (Cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, azonitriles such as 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2 ′ -Azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- ( 4-hydroxyphenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- ( -Phenylmethyl) propionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydro Chloride, 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2′-azobis [2- (2-imidazoline-2- Yl) propane], 2,2′-azobis (2,4,4-trimethylpentane), 2,2 -Alkylazo compounds such as azobis (2-methylpropane), other dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (4-cyanovaleric acid), 2,2 An azo compound such as' -azobis [2- (hydroxymethyl) propionate] can be exemplified.

  A decomposition accelerator can be used for the above-mentioned thermal radical curing agent. As the decomposition accelerator, N, N′-dimethylthiourea, tetramethylthiourea, N, N′-diethylthiourea, N, N′— Dibutylthiourea, benzoylthiourea, acetylthiourea, ethylenethiourea, N, N′-diethylenethiourea, N, N′-diphenylthiourea, N, N′-dilaurylthiourea, preferably tetramethylthiourea or benzoylthiourea An organometallic complex such as cobalt naphthenate, vanadium naphthenate, copper naphthenate, iron naphthenate, manganese naphthenate, cobalt stearate, vanadium stearate, copper stearate, iron stearate, manganese stearate; The alkyl group or alkylene group has 1 to 18 carbon atoms 1 to 3 alkylamines or alkylenediamines represented by integers, diethanolamine, triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethylphenol, 1,8-diazabicyclo (5,4,0) Undecene-7,1,8-diazabicyclo (5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) -nonene-5,6-dibutylamino-1,8-diazabicyclo (5 4,0) -undecene-7, amines such as 2-methylimidazole, 2-ethyl-4-methylimidazole; methacrylic phosphate, dimethycyl phosphate, monoalkyl acid phosphate, dialkyl phosphate, trialkyl phosphate, dialkyl phosphate Phosphate compounds such as phosphate and trialkyl phosphite; toluidine derivatives such as N, N-dimethyl-p-toluidine and N, N-diethyl-p-toluidine; N, N-dimethylaniline and N, N-diethylaniline An aniline derivative can be illustrated.

  As thermal cationic curing agents for polymerizing compounds having epoxy groups, oxirane rings such as oxetane rings, vinyl ethers, cyclic acetals, etc., sulfonium salts such as Sun-Aid SI-60, Sun-Aid SI-100, Sun-Aid SI-110L (all three new) Chemical Industry Co., Ltd.); a mixture of an aluminum complex and a compound having a silanol group (for example, Daicel Chemical Industry Co., Ltd., Daicat EX-1 (A), Daicat EX-1 (B) combination) As aluminum complexes, aluminum ethyl acetoacetate / diisopropylate, aluminum trisethylacetoacetate, aluminum alkyl acetoacetate / diisopropylate, aluminum bisethylacetoacetate / monoacetylacetonate, aluminum trisacetyl Examples of the compound having a silanol group such as acetonate or a precursor thereof include diphenylsilanediol, triphenylsilanol, silsesquioxane, and octamethylcyclotetrasiloxane.

  As a hydrazide-based curing agent for polymerizing a compound having an epoxy group or the like, adipic acid dihydrazide, 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-di Examples thereof include carbohydrazide and 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin].

  When an epoxy resin is polymerized using a hydrazide-based curing agent, various phenols can be added as accelerators, and as accelerators, bisphenol A, bisphenol AD, bisphenol F, phenol novolac, phenol novolac, cresol novolac And naphthol-modified phenol and dicyclopentadiene-modified phenol.

  As an acid anhydride curing agent for polymerizing a compound having an epoxy group or the like, glycerin bis (anhydrotrimellitate), ethylene glycol bis (anhydrotrimellitate), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4- Examples thereof include methylhexahydrophthalic anhydride and 3-methyltetrahydrophthalic anhydride.

  Examples of the polycarboxylic acid for polymerizing a compound having an epoxy group include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and the like.

  Examples of amine adduct curing agents for polymerizing a compound having an epoxy group include Ajinomoto Fine Techno Co., Amicure PN-23, Amicure PN-30, Amicure MY-24, Amicure MY-H, etc. Purity can be improved by using after washing with water.

  Examples of amine-based curing agents for polymerizing a compound having an epoxy group include metaphenylenediamine and diaminodiphenylmethane.

  As an imidazole-based curing agent for polymerizing a compound having an epoxy group or the like, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 ( 2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2 '-Ethyl, 4-methylimidazole (1')) ethyl-s Triazine, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid Additives, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3, 5-dicyanoethoxymethylimidazole, imidazole silane, etc. It can be illustrated.

  Examples of the imidazoline-based curing agent for polymerizing a compound having an epoxy group and the like include 2-methylimidazoline.

  Examples of the phenolic curing agent for polymerizing a compound having an epoxy group include a phenol novolac resin, a cresol novolac resin, a naphthol-modified phenol resin, a dicyclopentadiene-modified phenol resin, and the like.

  Other thermosetting agents for polymerizing epoxy groups include dicyandiamide, 6,6′-sulfonylbis [3,4-dihydro-3-phenyl-2H-1,3-benzoxazine], 3,3 ′-(methylenedi- 4,1-phenylene) bis [3,4-dihydro-2H-1,3-benzoxazine] and the like.

  The said thermosetting agent can also be used in combination of 2 or more, respectively.

  In the present invention, the photoinitiator molecule is attached to the particle, and the polymerizable compound and / or the thermosetting agent molecule may or may not be attached to the particle. It is preferable. By attaching polymerizable compound molecules and thermosetting agent molecules to the surface of the particles, the properties of the sealing agent and the interaction with the particles can be strengthened, the properties of the resin matrix can be improved, and the reactivity can be improved. . Examples of such a polymerizable compound molecule include a combination of a molecule having a thermosetting epoxy group and a molecule having a photocurable acrylic group, a combination of a molecule having an acrylic group and a molecule having a methacryl group. The reactivity can be enhanced by the presence of photoinitiator molecules and thermosetting agent molecules that can be polymerized in the vicinity of these molecules on the surface of one particle.

  The adhesion in the present invention means a state in which a photoinitiator molecule, optionally a polymerizable compound and / or a thermosetting agent molecule alone is chemically bonded or physically adsorbed to the particle surface, or a particle In the case of a layered compound, it indicates a state in which it is chemically bonded or physically adsorbed between the surface of the layered compound or between layers. Such adsorption occurs to some extent even if the particles and photoinitiator molecules are simply co-existing at the time of compounding, but it is difficult to adsorb most of the photoinitiator molecules in this state, so photoinitiation to the particles If the particle | grains to which the photoinitiator molecule | numerator adhered after adhering an agent molecule | numerator are not mix | blended with a sealing agent composition, a substantial effect will not be exhibited.

  Various substituents can be introduced into the photoinitiator, thermosetting agent and polymerizable compound in order to enhance the interaction with the particle surface or between the layers. For particles having a polar group such as a hydroxyl group on the surface, amino Group, imino group, amide group, hydroxy group, carboxyl group, silanol group, thiol group and the like can be exemplified, and for metal particles, disulfide, sulfide and the like can be further exemplified.

  For particles having a hydroxyl group on the surface, a compound having alkoxysilane or titanate can be used to chemically bond the compound to the particle surface.

  Moreover, a reactive part can also be exposed on the surface of hardened | cured material by making it harden | cure from the state which contained the photoinitiator and the thermosetting agent in the polymeric compound or the polymer melt | dissolved or melt | dissolved. For example, a composite of polyvinyl alcohol and a photo radical initiator can be pulverized and used.

  The sealant composition in the present invention includes a photoinitiator, a thermosetting agent, a particle having a photoinitiator molecule attached thereto, and a polymerizable compound (one attached to the particle or one not attached to the particle). Fillers, coupling agents, deterioration inhibitors, plasticizers, surfactants, solvents, additives such as pigments and dyes, and the like can be appropriately selected and blended as necessary.

  In the present invention, in addition to the type in which the photoinitiator is adhered to the particle surface, a photoinitiator that is not adhered to the particle is used in a small amount within the range where the effect of the present invention is exerted for the purpose of assisting polymerization. I can do it. In this case, in the case of the present invention, the amount of the photoinitiator not attached to the particles can be significantly reduced by using the type of photoinitiator attached to the particle surface. In particular, the type that becomes reactive after being cleaved after light irradiation generates a low molecular weight compound, and since such a compound has a large elution with respect to liquid crystals, it is particularly effective to improve display characteristics by reducing the addition amount. Can contribute.

  In the present invention, as the thermosetting agent, any of those not attached to the particle surface and those attached to the particle surface can be used, but preferably, the thermosetting agent is attached to the particle surface. In the case of this invention, the addition amount of the thermosetting agent which is not made to adhere to particle | grains can be reduced by using the type of thermosetting agent made to adhere to the particle | grain surface.

  In the present invention, filler particles to which a photoinitiator and a thermosetting agent are not attached can be used as optional components.

  In the present invention, a coupling agent can be included as an optional component, and ((tridecafluoro-1,1,2,2-tetrahydrooctyl) tri) as a fluorine-based silane coupling agent can be used as the coupling agent. Ethoxysilane, Shin-Etsu Chemical Co., Ltd. KBM-403 as an epoxy modified silane coupling agent, Toagosei Co., Ltd. TESOX as an oxetane modified silane coupling agent, or vinyltrimethoxysilane, vinyltriethoxysilane, γ- Chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ- Glycidoxypropyltrimethoxysilane Silane coupling agents such as β-glycidoxypropylmethyldimethoxysilane, γ-methacryloxyxypropyltrimethoxysilane, γ-methacryloxyxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, silane having imidazole group, , Triethanolamine titanate, titanium acetylacetonate, titanium ethyl acetoacetate, titanium lactate, titanium lactate ammonium salt, tetrastearyl titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, dicumyl phenyl Oxyacetate titanate, isopropyl trioctainol titanate, isopropyl dimethacrylisostearoyl titanate , Titanium lactate ethyl ester, octylene glycol titanate, isopropyl triisostearoyl titanate, triisostearyl isopropyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, tetra (2-ethylhexyl) titanate, butyl titanate dimer, isopropyl isostearoyl diacryl titanate, Isopropyltri (dioctylphosphate) titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1- Butyl) bis (di-tridecyl) phosphite titanate, bis ( Octyl pyrophosphate) oxyacetate titanate, it may be mentioned bis (dioctyl pyrophosphate) ethylene titanate, tetra -i- propyl titanate, tetra -n- butyl titanate, titanium-based coupling agents such as diisostearoyl ethylene titanate. These compounds can be exemplified by one type or a combination of two or more types as appropriate.

  Specific examples of the deterioration inhibitor in the present invention include 2,6-di-tert-butyl-phenol, 2,4-di-tert-butyl-phenol, 2,6-di-tert-butyl-4-ethyl- Phenol-based antioxidants exemplified by phenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butyl-anilino) -1,3,5-triazine and the like Agent: alkyldiphenylamine, N, N′-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-N′-isopropyl-p-phenylenediamine, etc. Aromatic amine antioxidants exemplified by: dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thio Sulfide hydroperoxide decomposition exemplified by dipropionate, bis [2-methyl-4- {3-n-alkylthiopropionyloxy} -5-tert-butyl-phenyl] sulfide, 2-mercapto-5-methyl-benzimidazole, etc. Agents: Tris (isodecyl) phosphite, phenyl diisooctyl phosphite, diphenyl isooctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate Phosphorus hydroperoxide decomposers exemplified by diethyl ester, sodium bis (4-tertiary-butylphenyl) phosphate, etc .; phenyl salicylate, 4-tertiary-octylphenyl salicyler Salicylate-based light stabilizers exemplified by, for example; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and other benzophenone-based light stabilizers; 2- (2′-hydroxy- 5′-methylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like Benzotriazole light stabilizers; hindered amine light stabilizers exemplified by phenyl-4-piperidinyl carbonate, bis- [2,2,6,6-tetramethyl-4-piperidinyl sebacate] and the like; 2,2′-thio-bis (4-t-octylphenolate)]-2-ethylhexylamine -Ni-type light stabilizers exemplified by nickel- (II); cyanoacrylate-type light stabilizers, oxalic acid anilide-type light stabilizers, and the like.

  In the present invention, a plasticizer can be blended, and as plasticizers, esters such as dioctyl phthalate, diisononyl adipate, trioctyl trimellitic acid, tricresyl phosphate, polyvinyl alcohol, rosin-modified phenolic resin, rosin ester, hydrogen And rosin such as fluorinated rosin resin and derivatives thereof.

  In the present invention, a surfactant can be blended, and as an anionic surfactant, soap, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate, polyoxyethylene alkyl ether phosphate, polyoxy Examples thereof include ethylene alkylphenyl ether phosphate, N-acyl amino acid salt, α-olefin sulfonate, alkyl sulfate ester salt, alkylphenyl ether sulfate ester, methyl taurate, and the like. Diaminoethylglycine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, fatty acid alkyl betaine, sulfobetaine, amino Nonionic (nonionic) surfactants include polyethylene glycol alkyl ester type compounds, alkyl ether type compounds such as triethylene glycol monobutyl ether, ester type compounds such as polyoxysorbitan ester, and alkylphenol types. A compound, a fluorine type compound, a silicone type compound, etc. are mentioned. These compounds can be used alone or in combination of two or more.

  In the present invention, a solvent can be blended. As the solvent, hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, amylbenzene, Turpentine oil, pinene, etc.), halogenated hydrocarbons (methyl chloride, chloroform, carbon tetrachloride, ethylene chloride, methyl bromide, ethyl bromide, chlorobenzene, chlorobromomethane, bromobenzene, fluorodichloromethane, dichlorodifluoromethane, difluorochloroethane, etc. ), Alcohol (methanol, ethanol, n-propanol, isopropanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, n-heptanol, 2-octanol, n-dodecanol, , Cyclohexanol, glycidol, etc.), ether, acetal (ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, ethyl benzyl ether, furan, furfural, 2-methyl furan, cineol, Methylal), ketones (acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-amyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone, acetophenone, etc.), esters (methyl formate, ethyl formate, propyl formate, methyl acetate, acetic acid) Ethyl, propyl acetate, acetic acid-n-amyl, methyl cyclohexyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl stearate, etc.), polyvalent alcohol And its derivatives (ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, etc.) , Fatty acids and phenols (formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, isovaleric acid, phenol, cresol, o-cresol, xylenol, etc.), nitrogen compounds (nitromethane, nitroethane, 1-nitropropane, nitrobenzene) , Monomethylamine, dimethylamine, trimethylamine, monoethylamine, diamylamine Aniline, monomethylaniline, o-toluidine, o-chloroaniline, dicyclohexylamine, dicyclohexylamine, monoethanolamine, formamide, N, N-dimethylformamide, acetamide, acetonitrile, pyridine, α-picoline, 2,4-lutidine , Quinoline, morpholine, etc.), sulfur, phosphorus, other compounds (carbon disulfide, dimethyl sulfoxide, 4,4-diethyl-1,2-dithiolane, dimethyl sulfide, dimethyl disulfide, methanethiol, propane sultone, triethyl phosphate, phosphorus Acid tophenyl, diethyl carbonate, ethylene carbonate, amyl borate, etc.), inorganic solvents (liquid ammonia, silicone oil, etc.), water and the like. Such a solvent can be used for adjusting the viscosity of the sealant composition and adjusting the electrical characteristics, particularly the dielectric constant.

Moreover, in order to confirm the application | coating condition of a frame sealing agent easily as needed, various pigment | dyes and pigments can also be mix | blended. Specific examples of pigments include titanium dioxide, barium sulfate, calcium carbonate, magnetic iron oxide, ultramarine, ultramarine, bitumen, zinc yellow, red rose, yellow lead, white lead, titanium white, carbon black, transparent iron oxide, aluminum Inorganic pigments such as powder, organic pigments such as azo, triphenylmethane, quinoline, anthraquinone, phthalocyanine, lake pigment, isoindoline pigment, quinacridone pigment, carbon black, metal colloid, etc. It is not limited to these. Examples of the dye include anthraquinone dyes, aminium dyes, polymethine dyes, diimonium dyes, cyanine dyes, phthalocyanine dyes, pyrazolone dyes, nigrosine dyes, anthraquinone dyes, azo dyes, chromium complex dyes, and the like. It is not limited. These dyes and pigments can be used alone or in combination of two or more. Such a dye can also be used in a state of being adsorbed on the particle surface.
The various compounds and additives described above are preferably selected from those that are difficult to dissolve in the liquid crystal.
The present invention further relates to a liquid crystal display device using the above-mentioned sealing agent composition and a method for producing a liquid crystal display device using the above-mentioned sealing agent composition, particularly a dropping method.

  EXAMPLES The present invention will be specifically described below using examples, but the present invention is not limited to these. The indication of the amount added is in parts by weight unless otherwise noted.

[Example 1]
In Example 1, a sealant composition was produced using photo / thermosetting particles produced by attaching photoinitiator and thermosetting agent molecules to the surface of silica nanoparticles.

(Production of photoinitiator and thermosetting agent-adhered particles)
As the particles, 100 parts of an organosilica sol (product name: MEK-ST, 30% dispersion of methyl ethyl ketone of silica particles having a particle diameter of 10 to 20 nm) manufactured by Nissan Chemical Industries, Ltd. As a photoinitiator, a photo radical initiator manufactured by Ciba Geigy ( Product name: 2 parts of Irgacure 369) and 1 part of imidazole silane (product name: IS-1000) manufactured by Nikko Metal Co., Ltd. as a thermosetting agent were placed in a 300 ml three-necked flask at 25 ° C. under light shielding conditions and argon atmosphere for 48 hours. Stir. After adding 100 parts of pure water and further stirring for 10 hours, the mixture was centrifuged (1 hour at 10000 r / m), the precipitate was collected, washed with 100 ml of methanol in a 300 ml three-necked flask, and then washed. The mixture was centrifuged (at 10000 r / m for 1 hour), and the precipitate was further collected and stirred and washed with 100 ml of methanol in a 300 ml three-necked flask. After repeating the said washing | cleaning 5 times, the deposit was vacuum-dried on 25 degreeC and light-shielding conditions for 24 hours, and the photoinitiator and the thermosetting agent adhesion particle (A-1) were obtained.

(Manufacture of partially acrylated epoxy resin)
100 parts of liquid bisphenol A type epoxy resin (product name: EPICLON-EXA-850CRP) manufactured by DIC Corporation, 25 parts of acrylic acid, 0.2 part of triphenylphosphine, and 0.1 part of hydroquinone are placed in a 300 ml three-necked flask, and an argon atmosphere Under heating at 90 ° C. for 5 hours. Thereafter, 0.7 part of xylenesulfonic acid was added, and the mixture was further stirred at 40 ° C. for 1 hour. In the state which heated the said reaction liquid to 40 degreeC, it extracted continuously with water using the liquid extractor (The limited company Kiriyama Seisakusho make: EX94A-1-4), and the electrical conductivity of the water layer was measured every 10 hours. . After washing with water for 30 hours, the product was further purified by continuous extraction until the rate of change in electrical conductivity was 3% or less. After removing the water layer by decantation, the water was completely removed by depressurization with a vacuum pump while bubbling with a mixed gas of dry nitrogen: oxygen = 95: 5 heated to 80 ° C., and the partially acrylated epoxy resin (B -1) (viscosity: 100,000 mPa · s) was obtained.

(Formulation of sealant composition)
Photoinitiator and thermosetting agent adhering particles (A-1) 20 parts, partially acrylated epoxy resin (B-1) 100 parts, Ajinomoto Fine Techno Co., Ltd. hydrazide thermosetting agent (product name: Amicure VDH) 15 parts Then, 2 parts of a silane coupling agent (product name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd. was placed in a planetary mixer with a cooling jacket and stirred until uniform to obtain a sealing agent composition (C-1).

[Example 2]
In Example 2, a sealant composition was produced using light / thermosetting particles produced by adhering a photoinitiator and a thermosetting agent to a clay layered compound by intercalation.

(Production of photoinitiator and thermosetting agent-adhered particles)
As particles, 20 parts of clay particles (trade name: Lucentite SWN; particle diameter: about 500 nm in a dry state) and 1500 parts of pure water were placed in a 2 liter beaker and stirred at 25 ° C. for 24 hours (mixed solution). 1).
As a photoinitiator, 1 part of 4,4′-bis (diethylamino) benzophenone and as a thermosetting agent, 1 part of 4-azidoaniline hydrochloride and 500 parts of pure water are placed in a 1 liter beaker and 1N hydrochloric acid is mixed. The solution was added until the pH of the solution reached 1 (mixed solution 2).
All of the liquid mixture 1 and liquid mixture 2 were added to a 3 liter three-necked flask, and the mixture was stirred for 48 hours at 25 ° C. in an argon atmosphere under light shielding conditions. The mixture was centrifuged (at 10000 r / m for 1 hour), the precipitate was collected, washed with 500 ml of pure water in a 3 liter three-neck flask, and then centrifuged (10000 r / m). m for 1 hour), and the precipitate was further collected and stirred and washed with 500 ml of pure water in a 3 liter three-necked flask. After repeating the said washing | cleaning 5 times, the deposit was vacuum-dried on 25 degreeC and light-shielding conditions for 24 hours, and the photoinitiator and the thermosetting agent adhesion particle (A-2) were obtained.

(Formulation of sealant composition)
Photoinitiator and thermosetting agent adhering particles (A-2) 10 parts, partially acrylated epoxy resin (B-1) 100 parts, Ajinomoto Fine Techno Co., Ltd. hydrazide thermosetting agent (product name: Amicure VDH) 15 parts Then, 2 parts of a silane coupling agent (product name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd. was placed in a planetary mixer with a cooling jacket and stirred until uniform to obtain a sealing agent composition (C-2).

Example 3
In Example 3, a sealant composition was produced using light / thermosetting particles produced by intercalating a photoinitiator, a thermosetting agent and a polymerizable compound to a clay layered compound.

(Production of photoinitiator, thermosetting agent and polymerizable compound-attached particles)
As particles, 20 parts of clay particles (trade name: Lucentite SWN; particle diameter: about 500 nm in a dry state) and 1500 parts of pure water were placed in a 2 liter beaker and stirred at 25 ° C. for 24 hours (mixed solution). 1).
As a photoinitiator, 1 part of 4,4′-bis (diethylamino) benzophenone, as a thermosetting agent, 1 part of 4-azidoaniline hydrochloride, as a polymerizable compound, an amino group-containing acrylate (product name) manufactured by Kyoeisha Chemical Industry Co., Ltd. : Light ester DE; molecular weight: 185.27) 1 part and 500 parts of pure water were placed in a 1 liter beaker, and 1N hydrochloric acid was added until the pH of the mixture became 1 (mixture 2).
All of the liquid mixture 1 and liquid mixture 2 were added to a 3 liter three-necked flask, and the mixture was stirred for 48 hours at 25 ° C. in an argon atmosphere under light shielding conditions. The mixture is centrifuged (at 10000 r / m for 1 hour), and the precipitate is collected and stirred and washed with 500 ml of pure water in a 3 liter three-necked flask, and then the mixture is centrifuged (at 10000 r / m). (1 hour), the precipitate was further collected and stirred and washed with 500 ml of pure water in a 3-liter three-necked flask. After repeating the said washing | cleaning 5 times, the deposit was vacuum-dried on 25 degreeC and light-shielding conditions for 24 hours, and the photoinitiator, the thermosetting agent, and polymeric compound composite particle (A-3) were obtained.

(Formulation of sealant composition)
Photoinitiator, thermosetting agent and polymerizable compound adhering particles (A-3) 15 parts, partially acrylated epoxy resin (B-1) 100 parts, hydrazide thermosetting agent (product name: Amicure manufactured by Ajinomoto Fine Techno Co., Ltd.) VDH) 5 parts, 2 parts of a silane coupling agent (product name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd. were placed in a planetary mixer with a cooling jacket, and stirred until uniform to obtain a sealant composition (C -3).

Example 4
In Example 4, a sealant composition was produced using light / thermosetting particles produced by adhering a photoinitiator and a thermosetting agent to a clay layered compound by intercalation.

(Production of photoinitiator and thermosetting agent-adhered particles)
As particles, 20 parts of clay particles (trade name: Lucentite SWN; particle diameter: about 500 nm in a dry state) and 1500 parts of pure water were placed in a 2 liter beaker and stirred at 25 ° C. for 24 hours (mixed solution). 1).
As a photoinitiator, 1 part of 4,4′-bis (diethylamino) benzophenone, as a thermosetting agent, 2 parts of a hydrazide thermosetting agent (product name: Amicure VDH) manufactured by Ajinomoto Fine Techno Co., Ltd., 1 part of 500 parts of pure water Into a liter beaker, 1N hydrochloric acid was added until the pH of the mixed solution reached 1 (mixed solution 2).
All of the liquid mixture 1 and liquid mixture 2 were added to a 3 liter three-necked flask, and the mixture was stirred for 48 hours at 25 ° C. in an argon atmosphere under light shielding conditions. The mixture is centrifuged (at 10000 r / m for 1 hour), and the precipitate is collected and stirred and washed with 500 ml of pure water in a 3 liter three-necked flask, and then the mixture is centrifuged (at 10000 r / m). (1 hour), the precipitate was further collected and stirred and washed with 500 ml of pure water in a 3-liter three-necked flask. After repeating the said washing | cleaning 5 times, the deposit was vacuum-dried on 25 degreeC and light-shielding conditions for 24 hours, and the photoinitiator and the thermosetting agent composite particle (A-4) were obtained.

(Formulation of sealant composition)
Photoinitiator, thermosetting agent and polymerizable compound adhering particles (A-4) 40 parts, partially acrylated epoxy resin (B-1) 100 parts, Shin-Etsu Chemical Co., Ltd. silane coupling agent (product name: KBM- 403) Two parts were put into a planetary mixer with a cooling jacket and stirred until uniform to obtain a sealant composition (C-4).

Example 5
In Example 5, a sealant composition was produced using photocurable particles produced by attaching a photoinitiator to nano-sized metal plate particles.

(Manufacture of photoinitiator particles)
To a 100 ml three-necked flask, 15 ml of pure water and 2 × 10 ⁻⁵ mol of silver nitrate were added to make a uniform solution. Thereto was added 1 × 10 ⁻⁴ mol of glycidylglycine and dissolved. The solution was stirred at 25 ° C. under an argon atmosphere for 30 minutes. The mixed solution was transferred to a Teflon pressure vessel having a capacity of 20 ml and heated at 160 ° C. for 24 hours. The precipitate generated in the mixed solution was washed with 100 ml of pure water, allowed to stand for 10 minutes, then the supernatant was decanted and the precipitate was washed with water. The washing with water was repeated 5 times, followed by vacuum drying at 25 ° C. for 24 hours to obtain a silver nanoplate. 1 g of silver nanoplate obtained in a 300 ml three-necked flask is dispersed in 100 g of pure water, 0.2 g of 4,4′-bis (diethylamino) benzophenone is added thereto and stirred for 1 hour, and then 1N hydrochloric acid is added to pH. Was added to 1, and the mixture was further stirred for 1 hour under light shielding in an argon atmosphere at 25 ° C. The mixture was allowed to stand for 10 minutes, and then the supernatant was removed by decantation. Further, 100 ml of pure water was added and the mixture was stirred and washed for 10 minutes. Then, the mixture was allowed to stand for 10 minutes to precipitate, and the supernatant was removed and the precipitate was washed with water. After repeating the said water washing 5 times, it vacuum-dried at 25 degreeC for 24 hours, and obtained the photoinitiator composite metal nanoplate (A-5).

(Formulation of sealant composition)
Photoinitiator-attached metal nanoplate (A-5) 2 parts, partially acrylated epoxy resin (B-1) 100 parts, Ajinomoto Fine Techno Co., Ltd. hydrazide thermosetting agent (product name: Amicure VDH), Shinetsu 2 parts of a silane coupling agent (product name: KBM-403) manufactured by Chemical Industry Co., Ltd. was placed in a planetary mixer with a cooling jacket, and stirred until uniform to obtain a sealant composition (C-5).

[Comparative Example 1]
In Comparative Example 1, a sealant composition was produced using a photoinitiator that was not attached to the particle surface.
As photoinitiators, Ciba Geigy photo radical initiator (product name; Irgacure 369) 2 parts, partially acrylated epoxy resin (B-1) 100 parts, Ajinomoto Fine Techno Co., Ltd. hydrazide thermosetting agent (product name : Amicure VDH) 15 parts, 2 parts of a silane coupling agent (product name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd. were placed in a planetary mixer with a cooling jacket, and stirred until uniform to obtain a sealant composition. (D-1).

[Comparative Example 2]
In Comparative Example 2, a sealant composition was produced in a state where the photoinitiator not adhered to the particle surface and the particles not adhered to the photoinitiator used in Example 2 were simply allowed to coexist in the composition.
As photoinitiators, Ciba Geigy photo radical initiator (product name; Irgacure 369) 2 parts, partially acrylated epoxy resin (B-1) 100 parts, Ajinomoto Fine Techno Co., Ltd. hydrazide thermosetting agent (product name : Amicure VDH) 15 parts, Shin-Etsu Chemical Co., Ltd. silane coupling agent (product name: KBM-403) 2 parts, Coop Chemical Co., Ltd. clay particles (trade name: Lucentite SWN; particle size: approx. In a dry state) (500 nm) 20 parts were put in a planetary mixer with a cooling jacket and stirred until uniform, and then stirred for 24 hours to obtain a sealant composition (D-2).

[Test example] (Characteristic evaluation)
Method of observing display spots A silica gap agent with a diameter of 4 μm was sprayed on a glass substrate with a 2 cm long, 2.5 cm wide, 0.5 mm thick TN liquid crystal alignment film and ITO. The sealant composition produced in Example 1 was applied to a square frame shape with a side of 1.8 mm, liquid crystal was dropped at the center, and then sandwiched between a glass substrate with ITO and an alignment film so as to face each other in a reduced-pressure atmosphere. It is. After the atmospheric pressure was reached, UV was irradiated at 300 mJ / cm ² (365 nm) to photocur the sealant. Subsequently, the test cell was produced by thermosetting at 120 ° C. for 1 hour. A DC voltage of 2.0 V was applied to the produced test cell, and it was confirmed with a polarizing microscope whether display spots were generated during sealing.

(Evaluation results)
Using the frame sealants of Examples 1 to 5 and Comparative Example 1, the test was performed by the above observation method. Spots generated in the liquid crystal part around the seal were visually observed and evaluated in the following three stages.
◎: No display spots ○: Almost no display spots △: Some display spots ×: Clear display spots

  According to the present invention, since elution of impurities derived from the photoinitiator into the liquid crystal can be suppressed, a liquid crystal display device with little deterioration in display characteristics can be obtained.

Claims (9)

  A sealant composition for a liquid crystal display device, comprising particles having one or more kinds of photoinitiator molecules attached thereto and one or more kinds of polymerizable compounds.   The sealant composition for a liquid crystal display device according to claim 1, wherein the particle is a clay layered compound.   The said particle | grain is a metal nanoplate, The sealing compound composition for liquid crystal display devices of Claim 1 or 2 characterized by the above-mentioned.   The liquid crystal display device according to claim 1, wherein one or more kinds of thermosetting agent molecules are further attached to the particles to which the one or more photoinitiator molecules are attached. Sealant composition.   5. The liquid crystal display according to claim 1, wherein the one or more kinds of polymerizable compound molecules are further attached to the particles to which the one or more photoinitiator molecules are attached. Sealant composition for apparatus.   6. The liquid crystal display according to claim 1, wherein the particle is a particle emitting fluorescence and / or phosphorescence, or a composite particle having fluorescent and / or phosphor material molecules attached thereto. Sealant composition for apparatus.   The said particle | grain has a particle diameter of 500 nm or less, The sealing compound composition for liquid crystal display devices in any one of Claims 1-6 characterized by the above-mentioned.   A method for producing a liquid crystal display device, comprising using the sealant composition for a liquid crystal display device according to any one of claims 1 to 7 as a sealant.   A liquid crystal display device using the sealant composition for a liquid crystal display device according to claim 1 as a sealant.