GB2279656A - Sealing compound for liquid crystal - Google Patents
Sealing compound for liquid crystal Download PDFInfo
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- GB2279656A GB2279656A GB9412354A GB9412354A GB2279656A GB 2279656 A GB2279656 A GB 2279656A GB 9412354 A GB9412354 A GB 9412354A GB 9412354 A GB9412354 A GB 9412354A GB 2279656 A GB2279656 A GB 2279656A
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- acrylate
- sealing compound
- liquid crystal
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1021—Polyurethanes or derivatives thereof
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1341—Filling or closing of cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0625—Polyacrylic esters or derivatives thereof
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
1 SEALING COMPOUND FOR LIQUID CRYSTAL 2279656 This invention relates to a
compound for sealing liquid crystal, and more particularly to sealing compounds for use in sealing the liquid crystal confined between electrode substrates for activating the liquid crystal.
A liquid crystal display unit in which liquid crystal is confined between transparent substrates having driving electrodes for activating the liquid crystal has been so far assembled in the manner as described below.
First, a sealing agent is applied to one of two substrates each having the liquid crystal driving electrode by a screen printing method or by using a dispenser, and the electrode substrates are placed one upon another while putting bead- or rod-like spacer elements therebetween. Then, the sealing agent between the substrates with electrodes is hardened under pressure to seal the liquid crystal between the substrates.
Conventionally, one-liquid thermosetting epoxy resin has been generally used as the sealing agent. Or, it has been proposed to use photo-setting or UV-setting adhesive consisting of epoxy acrylate for the sealing agent as a principal component (Japanese Patent Application Public Disclosure No. HEI 1-243029(A)).
Although the thermosetting adhesive conventionally used as the sealing agent has excellent moisture resistance, it consumes two or more hours to completely harden by heating, resulting in decrease of workability in assembling the liquid crystal display unit and so on.
Disadvantageously, there is a possibility that the electrode substrates between which the liquid crystal is confined do not precisely meet each other and cannot be held leaving a uniform gap therebetween.
On the other hand, the photo-setting or UV-setting resin which is hardened at room temperature for a short time does not easily cause lateral aberration or dislocation of the electrode substrates and is advantageous in assembling the liquid crystal display 2 - unit. However, the conventional adhesive consisting of epoxy acrylate adhesive is insufficient in adhesive strength for securing the substrates for confining the liquid crystal.
An adhesive agent consisting of polyether-denatured polyurethane acrylate or polyester-denatured polyurethane acrylate as a principal constituent possibly degrades light distribution efficiency required for conducting an experiment to evaluate the properties such as of moisture resistance of the adhesive.
Thus, a sealing agent possessing both properties of photo-setting and thermosetting functional group components has also been proposed, but it is very inferior in preservative stability to a one-fluid epoxy resin. Moreover, since this sealing agent should be exposed to ultraviolet rays, and heated to confine the liquid crystal between the electrode substrates when manufacturing the liquid crystal display unit. Thus, the sealing agent of functional group cannot also improve productivity of manufacturing the liquid crystal display unit.
An object of the present invention is to provide a sealing compound for use in sealing liquid crystal between electrode substrates for a liquid crystal display-unit, which has excellent heat resistance, moisture resistance and adhesive strength, and can hold in position the electrode substrates without causing dislocation and uneven separation.
To attain the object described above according to this invention, there is provided a sealing compound for sealing liquid crystal, which comprises essential components of (1) an acrylate resin, 0 a polymerizable component having at least one unsaturated radical, (3) a photopolymerizable initiator, and (a) an orienting component for ensuring orientation at high temperature in moist atmosphere.
There may be used polycarbonate-denatured polyurethane acrylate, or epoxy acrylate as the acrylate resin. As the polymerizable component having the unsaturated radical, 3 there may be used a monomer having at least one polymerizable unsaturated ethylene bond in one molecule, or an epoxy resin having at least one polymerizable glycidyl radical.
The orienting component may be composed of an inorganic filler, glycerol monomethacrylate, or isobornyl(meta)acrylate and potential thermosetting agent.
The sealing compound prepared by mixing the acrylate resin, polymerizable component having at least one unsaturated radical, photopolymerizable initiator with the orienting component has excellent heat-resistance and moisture-resistance, and can produce sufficient adhesive strength to precisely hold in parallel electrode substrates between which liquid crystal is confined and prevent dislocation of the substrates even at high temperature in moist atmosphere.
The sealing compound of this invention for sealing liquid crystal confined between the electrode substrates has excellent heat-resistance and moisture-resistance, and can produce sufficient adhesive strength to hold in position the electrode substrates. The sealing compound consists fundamentally of (1) an acrylate resin, Q a polymerizable component having at least one unsaturated radical, (3) a photopolymerizable initiator, and @ an orienting component for ensuring orientation at high temperature in moist atmosphere.
[EMBODIMENT 1] In a first embodiment, there are used polycarbonatedenatured polyurethane acrylate as the acrylate resin (1), a polymerizable monomer having at least one unsaturated ethylene bond in one molecule as the polymerizable component (2), and an inorganic filler as the orienting component (a). That is, the sealing compound of this embodiment comprises (1) the po lycarbonate- denatured polyurethane acrylate, (D the polymerizable monomer having at least one unsaturated ethylene bond, 03 the photopolymerizable initiator, and (4) the inorganic filler.
This sealing compound excels in the heat-resistance 4 - and moisture-resistance, and can produce sufficient adhesive strength. When this sealing compound is applied to electrode substrates of a liquid crystal display unit, the electrodes substrates can be secured in position 5 without suffering dislocation therebetween.
As the polycarbonate-denatured polyurethane acrylate, a compound can be prepared by selectively combining polycarbonate polyol, di-isocyanate and (meta)acrylate containing hydroxyl in accordance with purposes such as hardenability, viscosity, and flexibility, and is expressed by the following Formula (1):
HO [ R, Or],, R? OH is wherein, R, and R, denote the same or different bivalent hydrocarbon groups, or the same or different bivalent groups consisting of hydrocarbon groups bonded with each other by ether bond or ester bond, and n represents the number of 1 to 60 on average.
As the monomer (M having at least one unsaturated ethylene bond in one molecule used in this embodiment, there are 2-hydroxyethyl(meta)acrylate, 2-hydroxypropyle (meta)acrylate, 2-hydroxybutyl(meta)acrylate, trimethylolpropane- tri (meta) acryl ate, diethylene glycol -di (meta) acrylate, triethylene glycol-di(meta)acrylate, tetraethylene glycoldi(meta)acrylate, 1,2-propylene glycoldi(meta)acrylate, 1,2-propylene glycol -di (meta) acryl ate, 1,2-propylene glycol-di(meta)acrylate, 1,2propylene glycol-di(meta)acrylate, 1,2-propylene glycol-di(meta)acrylate, dipropylene glycol-di(meta)acrylate, digloceroltetra (meta) acryl ate, glycerin-tri (meta) acryl ate, isobornyl(meta)acrylate, 2phenoxyethyl(meta)acrylate, 2-phenoxyethyl(meta)acrylate, 3-hydroxy-3phenoxypropyle (meta) acryl ate, glycidol-dimethacrylate, penta-" erythritol, tetrahydrofurfuryl, 2-ethylhexyl(meta)acrylate, cyclohexyl(meta)acrylate, neopenthyl glycoldi(meta)acrylate, 1,6-hexanoldi(meta)acrylate, tri(meta)- acryloxy ethyl phosphite, allyl acrylate, n-vinyl pyrrolidone, and vinyl acetate.
As the photopolymerizable initiator 0 used in this embodiment, there may be used compounds, which produce a radical on exposure to ultraviolet rays, such as 1-hydroxy cyclohexyl phenylketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-l-lphenylpropane-l-on, 2-hydroxy-2-methyl-l-lphenylpropane-l-on, diethoxyaceto phenone, 2-methyl-l-(4-methylthiophenyl)-2-morpholino- propane-l-on, benzophenone, benzoin isopropyl ether, and methylphenyl glyoxylate.
As the inorganic filler @) in this embodiment, there may be used alumina, silica, barium sulphate, barium carbonate, strontium carbonate, calcium carbonate, talc, titanium oxide, and quartz power. Of these components, alumina can be preferably used, or two or more components may be composed.
The sealing compound consisting of the aforementioned components has excellent heat-resistance and moisture- resistance, and can produce large adhesive strength. Therefore, when this sealing compound is applied to electrode substrates between which liquid crystal is confined in a liquid crystal display unit, the electrodes substrates can be secured in position in parallel with a high accuracy without causing dislocation of the substrates even at hig temperature in moist atmosphere.
To further improve the adhesive properties of the sealing compound of the invention, there may be added a coupling agent for increasing the adhesive strength, and a spacer compound for adjusting the distance between the electrode substrates.
Furthermore, a phosphorus compound such as bis[(2hydroxyethyl)methacrylate)acid phosphite, a coloring agent such as dyes and pigment, polymerization inhibitor, oxidation inhibitor, leveling agent.
When the liquid crystal display unit is assembled by placing two transparent substrates with electrodes one on top the other by use of the sealing compound of the 6 present invention, the sealing compound is previously applied to one of the substrates by a screen printing method or by using a dispenser. Then, upon enclosing liquid crystal between the electrode substrates superposed upon each other, the sealing compound put between the electrode substrates is exposed to electron beam or ultraviolet rays to be hardened.
[EMBODIMENT 2] The sealing compound according to a second embodiment also consists fundamentally of (1) an acrylate resin, (Z) a polymerizable component having at least one unsaturated radical, (3) a photopolymerizable initiator, and (a) an orienting component for ensuring orientation at high temperature in moist atmosphere.
In this embodiment, there are used polycarbonate- denatured polyurethane acrylate as the acrylate resin (1), and polymerizable monomer having at least one unsaturated ethylene bond as the polymerizable component (2), similarly to the first embodiment described earlier. As the orienting component @, there can be used an inorganic filler, glycerol monomethacrylate, or isobornyl (meta)acrylate and potential thermosetting agent.
The inorganic filler serves to adjust the viscosity of the sealing compound.
According to this embodiment, the monomer contained therein becomes reluctant to volatilize after being applied to between the electrode substrates.
The polycarbonate-denatured polyurethane acrylate used in this embodiment may be of the compound as expressed by Formula (1) touched upon above. That is, it can be prepared by selectively combining polycarbonate polyol, di-isocyanate and (meta)acrylate containing hydroxyl in accordance with purposes such as hardenability, viscosity, and flexibility.
The polymerizable monomer (polymerizable component (2)) and the photopolymerizable initiator (3) in this second embodiment are the same as those enumerated above in the first embodiment.
The glycerol monomethacrylate used as the orienting component (3) is a compound expressed by the following Formula (2):
CH,=C-C-O-CH,-CH-CH,-OH... (2) 11 1 th U Ufl Similarly to the first embodiment noted above, there may be added a coupling agent for increasing the adhesive strength, a spacer compound for adjusting the distance between the electrode substrates, a phosphorus compound such as bis[(2hydroxyethyl)methacrylate]acid phosphite, a coloring agent such as dyes and pigment, polymerization inhibitor, oxidation inhibitor, and leveling agent to improve the general properties of the sealing compound.
The sealing compound in this embodiment can be applied for bonding the electrode substrates with each other for assembling the liquid crystal display unit in the same manner as in the first embodiment.
The sealing compound of this embodiment has not only excellent properties in heat-resistance, moistureresistance, and adhesive strength, but also an excellent function of making the monomer in the sealing compound reluctant to volatilize. Thus, the sealing compound of this embodiment brings about a marked effect such that, when this sealing compound is applied to electrode substrates between which liquid crystal is confined in a liquid crystal display unit, the electrode substrates can be held in position in parallel with a high accuracy without sufferring dislocation of the substrates even at high temperature in moist atmosphere. [EMBODIMENT 3] The sealing compound according to a third embodiment also consists of the fundamentally same compounds as those of the first and second embodiments described earlier.
That is, the sealing compound of this embodiment consists fundamentally of (1) an acrylate resin, (2) a polymerizable component having at least one unsaturated radical, (3) a photopolymerizable initiator, and (@ an orienting 8 component for ensuring orientation at high temperature in moist atmosphere. In this embodiment, the same photo polymerizable initiator as in the first and second embodiments is used.
In this embodiment, as the acrylate resin (1), epoxy acrylate is a composition to cause the sealing compound to be completely hardened by heating treatment for obtaining isotropic structure after primary hardening by exposure to light (ultraviolet rays). As the polymerizable component (a), an epoxy resin having at least one polymerizable glycidyl group in one molecule is used. As the orienting component @, isobornyl (meta)acrylate and a potential thermosetting agent are used.
The sealing compound of this embodiment has excellent properties in heat-resistance, moisture-resistance, and adhesive strength, and assures high stability of preservation, thus possibly heightening the productivity of the liquid crystal display unit.
The epoxy (meta)acrylate is a compound prepared by reacting an epoxy resin with a mixture of (meta)acrylate having a carboxyl group equivalent in weight to the epoxy group of the epoxy resin and polybasic acid.
As the (meta)acrylate, there are additive reactants of epoxy resin and (meta)acrylate or calboxyl group (meta)- acrylate, such as types of bisphenol-A diglycidyl ether, glycerin diglycidyl ether, polyalkylene glycol diglycidyl ether, polyacid diglycidyl ester, cyclohexiene oxide.
As the compound having at least one polymerizable glycidyl group in one molecule, an epoxy resin having at least one polymerizable glycidyl group, and an epoxy resin produced by open-cyclic polymerization of glycidyl group can be enumerated, but should not be understood as limitative.
As the epoxy resin in this embodiment, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenolAD type epoxy resin, epoxy resin fortified with water, novolac type epoxy resin, (mono)glycidyl ester type epoxy resin, polyurethane-denatured epoxy resin, nitrogen epoxy 9 resin having epoxidized methaxylene diamine, and rubberdenatured epoxy resin containing butadiene or NBR can be enumerated, but should not be understood as limitative.
The isobornyl (meta)acrylate used in the sealing compound of this embodiment is a compound expressed by the following structural Formulas (3) and (4).
1- CH3 1 C H:i CH3 CH3 CH3 1 U C; U C = C H 2 C H:3 CH3 0 C 0 C H - C 112 ..... (3) (4) The potential thermosetting agent used in this embodiment is a known compound such as dicyanogen diamide, dibasic acid hydrazides, imidazoles, imidazole epoxy adduct, and boron trifluoride amine complex.
Similarly to the second embodiment noted above, there may be added a coupling agent for increasing the adhesive strength, a spacer compound for adjusting the distance between the electrode substrates, a phosphorus compound such as bis[(2-hydroxyethyl)methacrylate]acid phosphite, a coloring agent such as dyes and pigment, polymerization inhibitor, oxidation inhibitor, leveling agent to improve the general properties of the sealing compound, and an inorganic filler serving to adjust the viscosity of the sealing compound.
The sealing compound in this embodiment can be applied to bond the electrode substrates with each other for assembling the liquid crystal display unit in the same manner as in the first and second embodiments.
The manner of assembling a liquid crystal display unit by use of the sealing compound of this embodiment comprises first exposing two transparent electrode substrates superposed upon each other across the sealing compound to light (ultraviolet rays) to primarily harden the sealing compound, introducing liquid crystal into between the electrode substrates, and heating the electrode substrates superposed upon each other across the sealing compound to be changed into an isotropic structure. Thus, the sealing compound can be completely hardened for a short time, and heighten the productivity of the liquid crystal display unit in comparison with a conventional production method using one-liquid thermosetting epoxy resin.
[EXPERIMENTAL EXAMPLES] The experiments of the Embodiments described above were attempted to verify the excellent properties of the sealing compounds according to the present invention.
The following Examples 1 to 6 (EX-1 to EX-6) correspond to the aforementioned first embodiment in which 11 various inorganic fillers are selectively added to polycarbonate- denatured polyurethane acrylate, the Examples 7 to 9 (EX-7 to EX-9) correspond to the aforementioned second embodiment in which glycerol monomethacrylate is added to polycarbonate-denatured polyurethane acrylate, and Examples 10 and 11 (EX-11 and EX-12) correspond to the aforementioned third embodiment in which isobornyl methacrylate is used as a thermosetting agent along with a photo(UV)-setting agent.
[EXAMPLES 1 TO 61 The sealing compounds of Examples 1 to 6 is characterized by adding various inorganic fillers to polycarbonate-denatured polyurethane acrylate. The contents and properties of these sealing compounds are shown in Table 1 below. Table 2 shows the contents and properties of comparative compounds. In particular, the first comparative compound (CM- 1) contains polyetherdenatured polyurethane acrylate, the second comparative compound (CM-2) contains polyester-denatured polyurethane acrylate, the third comparative compound (CM-3) contains polybutadiene- denatured polyurethane acrylate, the fourth compound (CM-4) contains epoxy acrylate, and the fifth comparative compound (CM-5) contains polycarbonatedenatured polyurethane acrylate with no inorganic filler.
TABLE 1
EX-1 EX-2 EX-3 EX-4 EX-5 EX-6 Polycarbonate-denatured polyurethane acrylate 60 60 60 60 60 60 Polyether-denatured polyurethane acrylate Polyester-denatured polyurethane acrylate Polybutadiene-denatured polyurethane acrylate Epoxy acrylate 2-hydroxymethyl-methacrylate 20 20 20 20 20 20 Isobornyl-methacrylate 20 20 20 20 20 20 2-hydroxy cyclohexyl-phenylketone 2 2 2 2 2 2 3-methacryloxy-propyle trimethoxysilane 1 1 1 1 1 1 Silica 5 3 Aluminc'i 20 50 50 Talc 20 Barium sulphate 20 1 1 - Viscosity (Pa.s) is 35 35 35 15 60 Moisture-permeability (g/m2.24h) 20 10 150 80 50 10 Screen printing property 0 0 0 0 0 0 9 Adhesive strength 0 0 0 0 0 0 Orientation (80tx1000h) 0 0 0 0 0 0 Orientation (60tx95%RHxlOO0h) 0 A A 0 Voltage holding ability (80'ex1000h) 0 0 0 0 0 0 Voltage holding ability (60'Cx9S%RHxlOO0h) 0 0 A A 0 0 1 1 1 1 1 1 Hardening Conditions: Illumination Remarks 0... Very excellent 0... Excellent A... Available X... Unavailable 10OW/cm2x30 seconds 1 3 - TABLE 2
EX-1 EX-2 EX-3 EX-4 EX-5 Polycarbonate-denatured polyurethane acrylate 60 Polyether-denatured polyurethane acrylate 60 Po-lyester-denatured polyurethane acrylate 60 Polybutadiene-denatured polyurethane acrylate 60 Epoxy acrylate 60 2-hydroxymethyl-methacrylate 20 20 20 20 20 Isobornyl-methacrylate 20 20 20 20 20 2-hydroxy cyclohexyl-phenylketone 2 2 2 2 2 3-methacryloxy-propyle-trimethoxysilane 1 1 1 1 1 Silica Alumina 50 50 50 50 Talc Barium sulphate Viscosity (Pa.s) 35 35 35 35 6 Moisture-permeability (g/m2.24h) 100 100 80 30200 Screen printing property 0 X Adhesive strength 0 0 X X Orientation (80Cx1000h) X A X 0 Orientation (600Cx95%RHxlOO0h) X X A A Voltage holding ability (80rx1000h) X A X 0 0 Voltage holding ability (60'ex95%RHxlOO0h) A X A 0 A 1 1 1 1 1 Hardening Conditions: Illumination 10OW/CM2 x30 Remarks ()... Very excellent 0... Excellent A... Available X... Unavailable seconds As is evident from Table 1, sealing compounds having excellent heat resistance, moisture resistance and adhesive strength can be obtained by use of polycarbonatedenatured polyurethane acrylate, and the moisturepermeability depends on the kind of the inorganic filler. Particularly, the moisture-permeability was improved by using alumina. Even when using the inorganic fillers other than silica, satisfactory properties could be obtained.
1 4 As is evident from Table 2, the comparative compounds CM-1 and CM-2 suffer from functional inefficiency in orientation and voltage holding ability, and are awkward particularly in the experimental results thereof. The comparative compounds CM-3 and CM-4 are insufficient in adhesive strength, thus disadvantageously causing flaking. The comparative compound CM5 entails problem such as difficulty in screen printing on an object such as electrode substrates for a liquid crystal display unit.
[EXAMPLES 7 TO 9] The sealing compounds of Examples 7 to 9 (EX7 to EX-9) prepared by adding glycerol monomethacrylate to polycarbonate-denatured polyurethane acrylate were tested to verify their fugacity, adhesive strength and orientation after being applied to the electrode substrates by screen printing by comparison with comparative compounds CM-7 to CM-9. The comparative compound CM-7 contains glycerol monomethacrylate.
The compound of Example 7 (EX-7) contains polyether- denatured polyurethane acrylate as a basic material. In Example 8 (EX-8), 2-hydroxy ethylmethacrylate is used instead of glycerol monomethacrylate. In Example 9 (EX-9), 2,2-bis[4-(methacryloxy-diethoxy)phenyl]propane is used.
The results of this evaluation test shown in Table 3 below.
1 5 TABLE 3
EX-7 EX-8 EX-9 CM-7 CM-8 CM-9 Polycarbonate-denatured polyurethane acrylate 60 60 60 60 60 Polyether-denatured polyurethane acrylate 60 Glycerol monomethacrylate 2-hydroxymethyl-methacrylate 40 20 20 40 2,2-bis[4-(methacryloxy-diethoxy) phenylpropane 20 40 2-hydroxy cyclohexyl-phenylketone 5 5 5 5 5 5 3-methacryloxy-propyle-trimethoxysilane 1 1 1 1 1 1 Alumina 50 50 50 50 50 50 Viscosity (Pa.s) 50 35 35 45 30 60 Moisture-permeability (g/m2.24h) 20 10 10 50 20 20 Screen printing property 0 0 X 0 Adhesive strength 0 0 0 X Orientation (80'Y,-x1000h) 0 0 0 Z25 0 0 Orientation (60rx95%RHx1000h) 0 0 X 0 Voltage holding ability (801Cx1000h) 0 A 0 0 Voltage holding ability (601Cx95%RHx1000h) 0 0 0 X 0 0 Hardening Conditions: Illumination 10OW/cm2)30 Remarks ()... Very excellent 0... Excellent A... Available X... Unavailable seconds According to the evaluation tests, it could be confirmed that the sealing compound of Example 7 (EX-7) in which glycerol monomethacrylate to polycarbonate-denatured polyurethane acrylate has an effect of decreasing the volatilization of the monomer after being applied to the electrode substrates even when being mixed with other monomer compositions.
On the other hand, the comparative compound CM-7 could also suppress volatilization of the monomer by using 10 glycerol monomethacrylate, but could not obtain sufficient 16 heat resistance and orientation after conducting a moisture resistance test.
In the test, when the electrode substrates were placed one upon another one hour after being applied with the comparative compound CM-8, the accurate distance between the electrode substrates could not been secured because the monomer of 2-hydroxy ethylmethacrylate was volatilized after being supplied by screen printing.
The comparative compound CM-9 using 2,2-bis[410 (methacryloxydiethoxy)phenyl]propane being high in boiling point could be suppress volatilization of the monomer, but could not obtain sufficient adhesive strength, consequently to cause flaking.
[EXAMPLES 10 AND 11] The sealing compounds of Examples 10 and 11 (EX-10 and EX-11) containing a thermosetting component of isobornyl methacrylate in addition to the photo(UV)-setting agent were tested to verify their excellent stability of preservation, adhesive strength and orientation.
The comparative compounds CM-10 and CM-11 used under the comparative tests contain 2-hydroxyethyl-methacrylate instead of isobornyl methacrylate.
The results of the tests are shown in Table 4 below.
17 TABLE 4
Epoxy acrylatel Isobornyl-methacrylate 2-hydroxymethyl-methacrylate 2hydroxy cyclohexyl-phenylketone Epikoto #807 Novacure 3971HPXO Glycidyl trimethoxysilan Alumina 20 3 30 30 1 so 10 > 3mon. 0 0 EX-11 35 3 10 20 1 50 13 > 3mon.
CM-10 3 30 30 1 50 20 days 0 X 0 X 0 seconds CM-11 3 30 30 1 so 1 Viscosity (Pa.s) Moisture-permeability (g/m2.24h) Stability in preservation (25'C,) Adhesive strength Orientation (80'Cx1000h) Orientation (60rx95%RHx1000h) Voltage holding ability (801Cx1000h) Voltage holding ability (60"(-,x95%RHxlOO0h) 0 0 25 days 0 X 0 X Hardening Conditions: Illumination 10OW/cm2x30 Remarks ()... Very excellent 0... Excellent A... Available X... Unavailable 1... Trade name of Three Bond Co., Ltd.
As shown in Table 4, the sealing compounds of Examples 10 and 11 are different in compounding ratio of the photo(UV)-setting agent and the thermosetting agent. However, since these sealing compounds uses isobornyl methacrylate as a monomer, the stability of preservation can be maintained over three months at room temperature. Thus, the sealing compounds of these embodiments can be applied practically. Furthermore, these sealing compounds after hardening within the liquid crystal display unit could ensure sufficient heat-resistance and moistureresistance for a long time.
18 On the contrary, the comparative compounds CM-10 and CM-11 were extremely lowered in stability of preservation in the test. When the comparative compounds primarily hardened by exposure to light (ultraviolet rays) were further hardened by heating for obtaining isotropic structure after enclosing liquid crystal in between the electrode substrates, they were degraded in orientation.
As is apparent from the foregoing description, the sealing compound according to this invention, which comprises essential components of an acrylate resin, a polymerizable component having at least one unsaturated radical, a photopolymerizable initiator, and an orienting component for ensuring orientation at high temperature in moist atmosphere, can be applied for tightly enclosing liquid crystal between electrode substrates for a liquid -crystal display unit while ensuring excellent heat resistance, moisture resistance and adhesive strength without causing dislocation and uneven separation of the electrode substrates.
As can be readily appreciated, it is possible to deviate from the above embodiments of the present invention and, as will be readily understood by those skilled in this art, the invention is capable of many modifications and improvements within the scope and spirit thereof. Accordingly, it will be understood that the invention i-s not to be limited by these specific embodiments, but only by the scope and spirit of the appended claims.
19
Claims (9)
1. A sealing compound for liquid crystal, which comprises an acrylate resin, a polymerizable component having at least one unsaturated radical, a photopolymerizable initiator, and an orienting component for ensuring orientation at high temperature in moist atmosphere.
2. A sealing compound according to claim 1, wherein said polycarbonatedenatured polyurethane acrylate is a compound prepared by selectively combining polycarbonate polyol, di-isocyanate and (meta)acrylate containing hydroxyl.
3. A sealing compound according to claim 1, wherein said acrylate resin is polycarbonate-denatured polyurethane acrylate.
4. A sealing compound according to claim 1, wherein said acrylate resin is epoxy acrylate.
5. A sealing compound according to claim 1, wherein said polymerizable component is a polymerizable monomer having at least one unsaturated ethylene bond in one molecule.
6. A sealing compound according to claim 1, wherein said polymerizable component is an epoxy resin having at least one polymerizable glycidyl group in one molecule.
7. A sealing compound according to claim 1, wherein said orienting component is an inorganic filler, glycerol monomethacrylate, or isobornyl(meta)acrylate and potential thermosetting agent.
- 20
8. A sealing compound according to claim 7, wherein said inorganic filler is alumina, silica, barium sulphate, barium carbonate, strontium carbonate, calcium carbonate, talc, titanium oxide, or quartz power.
9. A sealing compound substantially as hereinbefore described in any one of Embodiments 1 - 3 or any one of Examples 1 - 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5173675A JP3024440B2 (en) | 1993-06-22 | 1993-06-22 | Liquid crystal sealant |
| JP17367393A JPH0713173A (en) | 1993-06-22 | 1993-06-22 | Sealing agent for liquid crystal |
| JP17367493A JPH0713174A (en) | 1993-06-22 | 1993-06-22 | Sealing agent for liquid crystal |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9412354D0 GB9412354D0 (en) | 1994-08-10 |
| GB2279656A true GB2279656A (en) | 1995-01-11 |
| GB2279656B GB2279656B (en) | 1997-04-09 |
Family
ID=27323823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9412354A Expired - Fee Related GB2279656B (en) | 1993-06-22 | 1994-06-20 | Sealing compound for liquid crystal |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR950001363A (en) |
| DE (1) | DE4421621A1 (en) |
| GB (1) | GB2279656B (en) |
| TW (1) | TW351729B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0730188A2 (en) * | 1995-03-01 | 1996-09-04 | Matsushita Electric Industrial Co., Ltd | Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| EP0819714A1 (en) * | 1996-07-17 | 1998-01-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Photosensitive resin composition for photo-cast-molding |
| US6001203A (en) * | 1995-03-01 | 1999-12-14 | Matsushita Electric Industrial Co., Ltd. | Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| EP2680064A1 (en) * | 2012-06-29 | 2014-01-01 | InnoLux Corporation | Liquid-crystal display |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI395027B (en) * | 2009-05-01 | 2013-05-01 | Ind Tech Res Inst | Sealant composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59137929A (en) * | 1983-01-28 | 1984-08-08 | Matsushita Electric Ind Co Ltd | Sealing material for liquid crystal display panel |
| JPS6283720A (en) * | 1985-10-08 | 1987-04-17 | Dainippon Ink & Chem Inc | Liquid crystal display element |
| JPH01243029A (en) * | 1988-03-24 | 1989-09-27 | Seiko Epson Corp | Liquid crystal display panel |
| EP0503834A2 (en) * | 1991-03-08 | 1992-09-16 | National Starch and Chemical Investment Holding Corporation | Liquid crystal display device |
| JPH05295087A (en) * | 1992-04-17 | 1993-11-09 | Kyoritsu Kagaku Sangyo Kk | Frame sealing agent composition for liquid crystal display |
| GB2272906A (en) * | 1992-11-18 | 1994-06-01 | Sharp Kk | Sealing material for liquid crystal display panel, and liquid crystal display panel using it |
-
1994
- 1994-06-20 TW TW083105546A patent/TW351729B/en active
- 1994-06-20 GB GB9412354A patent/GB2279656B/en not_active Expired - Fee Related
- 1994-06-21 DE DE4421621A patent/DE4421621A1/en not_active Withdrawn
- 1994-06-22 KR KR1019940014228A patent/KR950001363A/en not_active Application Discontinuation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59137929A (en) * | 1983-01-28 | 1984-08-08 | Matsushita Electric Ind Co Ltd | Sealing material for liquid crystal display panel |
| JPS6283720A (en) * | 1985-10-08 | 1987-04-17 | Dainippon Ink & Chem Inc | Liquid crystal display element |
| JPH01243029A (en) * | 1988-03-24 | 1989-09-27 | Seiko Epson Corp | Liquid crystal display panel |
| EP0503834A2 (en) * | 1991-03-08 | 1992-09-16 | National Starch and Chemical Investment Holding Corporation | Liquid crystal display device |
| JPH05295087A (en) * | 1992-04-17 | 1993-11-09 | Kyoritsu Kagaku Sangyo Kk | Frame sealing agent composition for liquid crystal display |
| GB2272906A (en) * | 1992-11-18 | 1994-06-01 | Sharp Kk | Sealing material for liquid crystal display panel, and liquid crystal display panel using it |
Non-Patent Citations (4)
| Title |
|---|
| WPI Abstract Accession No 84-233493/38 & JP 59137929 A * |
| WPI Abstract Accession No 87-146729/21 & JP 62083720 A * |
| WPI Abstract Accession No 89-327895/45 & JP 01243029 A * |
| WPI Abstract Accession No 93-392738/49 & JP 05295087 A * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0730188A2 (en) * | 1995-03-01 | 1996-09-04 | Matsushita Electric Industrial Co., Ltd | Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| EP0730188A3 (en) * | 1995-03-01 | 1998-07-15 | Matsushita Electric Industrial Co., Ltd | Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| US5898041A (en) * | 1995-03-01 | 1999-04-27 | Matsushita Electric Industrial Co., Ltd. | Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| US6001203A (en) * | 1995-03-01 | 1999-12-14 | Matsushita Electric Industrial Co., Ltd. | Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| US6013339A (en) * | 1995-03-01 | 2000-01-11 | Matsushita Electric Industrial Co., Ltd. | Liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display |
| EP0819714A1 (en) * | 1996-07-17 | 1998-01-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Photosensitive resin composition for photo-cast-molding |
| EP0957120A1 (en) * | 1996-07-17 | 1999-11-17 | Asahi Kasei Kogyo Kabushiki Kaisha | Process of manufacture of a photo-cast molding |
| US5990190A (en) * | 1996-07-17 | 1999-11-23 | Asahi Kasei Kogyo Kabushiki Kaisha | Photosensitive resin composition for photo-cast-molding |
| EP2680064A1 (en) * | 2012-06-29 | 2014-01-01 | InnoLux Corporation | Liquid-crystal display |
| US9285637B2 (en) | 2012-06-29 | 2016-03-15 | Innolux Corporation | Liquid-crystal display |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9412354D0 (en) | 1994-08-10 |
| TW351729B (en) | 1999-02-01 |
| GB2279656B (en) | 1997-04-09 |
| DE4421621A1 (en) | 1995-02-02 |
| KR950001363A (en) | 1995-01-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20030620 |