WO2016013214A1 - 液晶シール剤、および液晶表示パネルの製造方法 - Google Patents
液晶シール剤、および液晶表示パネルの製造方法 Download PDFInfo
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- WO2016013214A1 WO2016013214A1 PCT/JP2015/003662 JP2015003662W WO2016013214A1 WO 2016013214 A1 WO2016013214 A1 WO 2016013214A1 JP 2015003662 W JP2015003662 W JP 2015003662W WO 2016013214 A1 WO2016013214 A1 WO 2016013214A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/06—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- 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
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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
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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
- G02F1/1341—Filling or closing of cells
Definitions
- the present invention relates to a liquid crystal sealant and a method for producing a liquid crystal display panel using the same.
- liquid crystal display panels have been widely used as image display panels for various electronic devices such as mobile phones and personal computers.
- the liquid crystal display panel has a structure in which a liquid crystal material (hereinafter simply referred to as “liquid crystal”) is sandwiched between two transparent substrates having electrodes provided on the surface, and the periphery thereof is sealed with a sealing member.
- liquid crystal a liquid crystal material
- the liquid crystal sealing agent for obtaining the sealing member is in direct contact with the liquid crystal although the amount used is small, and thus greatly affects the reliability of the liquid crystal display panel. Therefore, in order to realize high image quality of the liquid crystal display panel, the liquid crystal sealant is required to have advanced and various characteristics.
- the liquid crystal injection method includes (1) applying a liquid crystal sealant to the inner edge of one transparent substrate to form a frame, and (2) drying the liquid crystal sealant by precuring the substrate. The other substrate is bonded, and (3) the two substrates are heated and pressed to bond the substrates together to form a frame (cell) of the liquid crystal sealant between the substrates. (4) A method of manufacturing a liquid crystal display panel by injecting an appropriate amount of liquid crystal into an empty cell and then sealing the liquid crystal injection port.
- liquid crystal dropping method has been studied as a method for manufacturing a liquid crystal display panel which is expected to improve productivity.
- a liquid crystal sealant is applied to the inner edge of a transparent substrate to form a frame for filling liquid crystal
- liquid crystal is dropped into the frame
- liquid crystal sealant Is a method of manufacturing a panel by superposing two substrates in an uncured state under high vacuum and then curing the liquid crystal sealant.
- a light and thermosetting liquid crystal sealant may be used.
- the liquid crystal sealant for example, in the step (3), after the liquid crystal sealant is temporarily cured by irradiating light such as ultraviolet rays, post-curing by heating is performed.
- liquid crystal sealing agent for the liquid crystal dropping method for example, it has been proposed to use a liquid epoxy resin (Patent Document 1).
- a liquid epoxy resin Patent Document 1
- rubbery components, etc. in order to improve the adhesion of the liquid crystal sealant or improve the stress relaxation properties, it is possible to add rubbery components, etc., and to increase the heat resistance of the liquid crystal sealant, filling with glass fibers or glass particles.
- an agent Patent Document 2
- a liquid crystal sealing agent containing resin fine particles having a core-shell structure has also been proposed (Patent Document 3).
- Patent Documents 4 to 6 It has also been proposed to add an organic filler having a particle size larger than the cell gap to the liquid crystal sealant.
- an organic filler having a large particle diameter is sandwiched between two substrates, the organic filler is compressed and closes the gap between the two substrates without any gaps, so liquid crystal leaks (liquid crystal enters the liquid crystal seal, Leaking through the liquid crystal seal is likely to be suppressed.
- the present invention provides a liquid crystal sealant that has a uniform line width even when the seal pattern is thinned, can bond two substrates with high adhesive strength, and does not easily cause liquid crystal leakage. Objective.
- the first of the present invention relates to the following liquid crystal sealant.
- [1] (1a) (meth) acrylic resin, or (1b) (meth) acryl-modified epoxy resin having an epoxy group and (meth) acrylic group in the molecule, and (2) an organic filler having an average particle size of 4 to 13 ⁇ m A, (3) an organic filler B having an average particle size of 0.05 to 1 ⁇ m, and (4) a radical polymerization initiator, wherein the content (mass) of the component (2) is W1, and the component ( 3) A liquid crystal sealant that satisfies 0.25 ⁇ W1 / (W1 + W2) ⁇ 0.75 when the content (mass) of 3) is W2.
- the total amount of the component (2) and the component (3) is 20 to 100 parts by mass with respect to 100 parts by mass of the resin unit including the component (1a) and the component (1b).
- Each of the component (2) and the component (3) is one or more kinds of fine particles selected from the group consisting of silicone fine particles, acrylic fine particles, styrene fine particles, and polyolefin fine particles, [1] to [3] Liquid crystal sealing agent in any one of.
- the content of the component (4) is 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the resin unit including the component (1a) and the component (1b).
- [6] (5) The content of the component (5) is 3 to 30% by mass with respect to 100 parts by mass of the resin unit including the component (1a) and the component (1b).
- the content of the component (6) is 3 to 30 parts by mass with respect to 100 parts by mass of the resin unit further including the inorganic filler and combining the components (1a) and (1b).
- [8] (7) Further containing a light-shielding agent, and the content of the component (7) is 3 to 30 parts by mass with respect to 100 parts by mass of the resin unit in which the (1a) and (1b) are combined.
- the second of the present invention relates to a liquid crystal sealant shown below.
- a step of dropping a liquid crystal on the other substrate paired with the one substrate, a step of superimposing the one substrate on the other substrate, and a step of curing the seal pattern And a method for manufacturing a liquid crystal display panel.
- the liquid crystal sealing agent of the present invention is used for forming a sealing member of a liquid crystal display panel, and the line width is likely to be uniform even if the line width is reduced. As a result, the strength of the seal pattern and the cured product (seal member) of the liquid crystal sealant is likely to be uniform, and liquid crystal leaks are unlikely to occur. Furthermore, the adhesive strength between the sealing member and the substrate is also high. Therefore, a highly reliable liquid crystal display panel, and thus a highly reliable liquid crystal display device can be obtained.
- the liquid crystal sealant of the present invention includes (1) a resin, (2) two types of organic fillers having different average particle diameters, and (3) a radical polymerization initiator.
- the liquid crystal sealing agent may contain (4) an epoxy curing agent, (5) an inorganic filler, (6) an epoxy resin, (7) a light shielding agent, and the like as necessary.
- the line width is difficult to be uniform, and a portion having a narrow line width is likely to occur locally. And when the internal pressure was applied to the said location, the liquid crystal leaked or the sealing member and the substrate were easily peeled off.
- the liquid crystal sealant of the present invention includes two types of organic fillers having different average particle diameters; that is, an organic filler A having a relatively large average particle diameter and an organic filler B having a relatively small average particle diameter. . Then, the organic filler A having a relatively large average particle diameter is crushed between the two substrates of the liquid crystal display panel to fill these gaps without any gaps. On the other hand, the organic filler B having a relatively small average particle diameter fills the gap between the organic fillers A. Therefore, the line width of the seal pattern is likely to be uniform, and it is difficult to produce a locally low strength region. Moreover, since the organic filler B has a high stress relaxation capability, the adhesive strength of the sealing member obtained by curing the liquid crystal sealing agent is likely to increase. That is, according to the liquid crystal sealant of the present invention, a highly reliable liquid crystal display panel is obtained in which liquid crystal leakage is small and the substrate is difficult to peel off.
- the liquid crystal sealant contains at least (1a) (meth) acrylic resin, or (1b) (meth) acrylic-modified epoxy resin having an epoxy group and (meth) acrylic group in one molecule. It is. These may be included alone or in combination of two or more. When (1b) (meth) acrylic-modified epoxy resin is contained in the liquid crystal sealant, the moisture resistance of the cured product (seal member) of the liquid crystal sealant is increased.
- the (meth) acrylic resin contains one or more (meth) acrylic groups.
- (Meth) acryl represents that either methacryl or acrylic may be used.
- the (meth) acrylic resin may be a monomer of a compound having a (meth) acrylic group, or may be an oligomer or a polymer. However, the compound which has an epoxy group in (1a) (meth) acrylic resin is not included.
- Examples of (meth) acrylic resins include diacrylates and / or dimethacrylates such as polyethylene glycol, propylene glycol, and polypropylene glycol; diacrylates and / or dimethacrylates of tris (2-hydroxyethyl) isocyanurate; Diacrylate and / or dimethacrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of pentyl glycol; of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A Diacrylate and / or dimethacrylate; trimethylolpropane obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane Di- or triacrylate and / or di- or trimethacrylate of diol; Diacrylate and / or dimethacrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of
- the weight average molecular weight of the (1a) (meth) acrylic resin may be, for example, about 310 to 1000.
- the weight average molecular weight Mw of the (meth) acrylic resin can be measured (polystyrene conversion) by, for example, gel permeation chromatography (GPC).
- the amount of (1a) (meth) acrylic resin contained in the liquid crystal sealant is 0 to 80 parts by mass with respect to 100 parts by mass of the liquid crystal sealant, although it depends on the required curability of the liquid crystal sealant.
- the amount is preferably 0 to 60 parts by mass.
- the (meth) acryl-modified epoxy resin is preferably a (meth) acryl-modified epoxy resin obtained by reacting an epoxy resin and (meth) acrylic acid, for example, in the presence of a basic catalyst.
- the (1b) (meth) acrylic-modified epoxy resin since the (1b) (meth) acrylic-modified epoxy resin has an epoxy group and a (meth) acrylic group in the molecule, it can have both photocuring property and thermosetting property. Furthermore, even if the (1b) (meth) acrylic-modified epoxy resin is derived from an amorphous epoxy resin, the resin contains a hydroxyl group generated by a reaction with (meth) acrylic acid. Dissolution can be sufficiently suppressed.
- the epoxy resin used as a raw material for the (meth) acryl-modified epoxy resin may be a bifunctional or higher functional epoxy resin having two or more epoxy groups in the molecule, such as bisphenol A type, bisphenol F type, 2, 2 Bisphenol type epoxy resins such as' -diallyl bisphenol A type, bisphenol AD type and hydrogenated bisphenol type; novolac type epoxy resins such as phenol novolak type, cresol novolak type, biphenyl novolak type, and trisphenol novolak type; biphenyl type epoxy Resin; Naphthalene type epoxy resin and the like are included.
- bisphenol A type bisphenol F type
- 2, 2 Bisphenol type epoxy resins such as' -diallyl bisphenol A type, bisphenol AD type and hydrogenated bisphenol type
- novolac type epoxy resins such as phenol novolak type, cresol novolak type, biphenyl novolak type, and trisphenol novolak type
- biphenyl type epoxy Resin Naphthalene type epoxy resin and
- a (meth) acryl-modified epoxy resin obtained by (meth) acryl modification of a trifunctional or tetrafunctional polyfunctional epoxy resin has a high crosslink density, and the adhesive strength between the sealing member and the substrate is likely to decrease. Therefore, a (meth) acryl-modified epoxy resin obtained by (meth) acryl modification of a bifunctional epoxy resin is preferable.
- the bifunctional epoxy resin is preferably a biphenyl type epoxy resin, a naphthalene type epoxy resin, or a bisphenol type epoxy resin.
- bisphenol type epoxy resins such as bisphenol A type and bisphenol F type are preferable from the viewpoint of application efficiency of the liquid crystal sealant. Is preferred.
- Bisphenol type epoxy resins have advantages such as excellent coating properties compared to biphenyl ether type epoxy resins.
- the epoxy resin used as a raw material may be one type or a combination of two or more types. Moreover, it is preferable that the epoxy resin used as a raw material is highly purified by a molecular distillation method, a washing method, or the like.
- the weight average molecular weight of the (meth) acryl-modified epoxy resin can be, for example, about 310 to 1000.
- the weight average molecular weight Mw of the (meth) acryl-modified epoxy resin can be measured (polystyrene conversion) by, for example, gel permeation chromatography (GPC).
- the amount of the (1b) (meth) acrylic-modified epoxy resin contained in the liquid crystal sealant is preferably 0 to 80 parts by mass and preferably 0 to 60 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. More preferred.
- the above-mentioned (1a) (meth) acrylic resin and (1b) (meth) acryl-modified epoxy resin preferably contain a hydrogen-bonding functional group such as a hydroxyl group, a urethane bond, an amide group, or a carboxyl group.
- a hydrogen-bonding functional group such as a hydroxyl group, a urethane bond, an amide group, or a carboxyl group.
- the hydrogen bondable functional group also include a hydroxyl group generated by the reaction of the epoxy group of the epoxy resin with (meth) acrylic acid.
- a (meth) acrylic resin and (1b) a (meth) acrylic acid which is a raw material for a (meth) acryl-modified epoxy resin, a hydroxyl group, a urethane bond, a carboxyl group, an amide group, etc. contained in the epoxy resin. It is.
- the (1a) (meth) acrylic resin and the (1b) (meth) acrylic-modified epoxy resin contain a hydrogen bonding functional group, the compatibility between the resin and the hydrophobic liquid crystal material is lowered. As a result, the liquid crystal sealant is hardly dissolved in the liquid crystal material, and a liquid crystal sealant suitable for the liquid crystal dropping method is obtained.
- the hydrogen bonding functional group equivalents of (1a) (meth) acrylic resin and (1b) (meth) acrylic modified epoxy resin contained in the liquid crystal sealant are both 1.0 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 3 mol. / G, more preferably 2.0 ⁇ 10 ⁇ 3 to 4.5 ⁇ 10 ⁇ 3 mol / g.
- the hydrogen-bonding functional group equivalent is less than 1.0 ⁇ 10 ⁇ 4 mol / g, hydrogen bonds contained in one molecule of (1a) (meth) acrylic resin or one molecule of (1b) (meth) acryl-modified epoxy resin
- the number of functional functional groups is small, and it is difficult to obtain a dissolution inhibiting effect on liquid crystals.
- the hydrogen bondable functional group equivalent exceeds 5 ⁇ 10 ⁇ 3 mol / g, the moisture resistance of the cured product of (1a) (meth) acrylic resin or (1b) (meth) acrylic modified epoxy resin tends to decrease.
- the hydrogen-bonding functional group equivalent (mol / g) of (1a) (meth) acrylic resin and (1b) (meth) acryl-modified epoxy resin is “one molecule of (1a) (meth) acrylic resin or (1b) ( The number of hydrogen-bonding functional groups contained in the (meth) acryl-modified epoxy resin "/" weight average molecular weight (Mw) of (1a) (meth) acrylic resin or (1b) (meth) acryl-modified epoxy resin " .
- the hydrogen-bonding functional group contained in the (meth) acryl-modified epoxy resin is only a hydroxyl group generated by the reaction between (meth) acrylic acid and the epoxy resin
- the number of moles of reacted (meth) acrylic acid is , By dividing by the weight average molecular weight (Mw) of the (meth) acryl-modified epoxy resin.
- the hydrogen bondable functional group equivalent of (1a) (meth) acrylic resin is adjusted by the number of hydrogen bondable functional groups contained in the (meth) acrylic resin.
- the hydrogen bondable functional group equivalent of (1b) (meth) acryl-modified epoxy resin is, for example, adjusting the number of moles of (meth) acrylic acid reacted with the raw material epoxy resin; It can be controlled by adjusting the amount of the hydrogen-bonding functional group of acrylic acid or epoxy resin.
- the hydroxyl value equivalent of the (meth) acryl-modified epoxy resin is particularly preferably 2.0 ⁇ 10 ⁇ 3 to 5 ⁇ 10 ⁇ 3 mol / g.
- the total content of (1a) (meth) acrylic resin and (1b) (meth) acrylic-modified epoxy resin with respect to 100 parts by mass of the liquid crystal sealant is preferably 40 to 80 parts by mass, and 50 to 75 parts by mass It is more preferable that
- the liquid crystal sealant contains an organic filler A having an average particle size of 4 to 13 ⁇ m and an organic filler B having an average particle size of 0.05 to 1 ⁇ m.
- the average particle diameter of the organic filler A is preferably 4 to 10 ⁇ m, more preferably 5 to 8 ⁇ m.
- the average particle size of the organic filler B is preferably 0.1 to 0.8 ⁇ m, and more preferably 0.1 to 0.6 ⁇ m.
- the average particle size of the filler can be measured by microscopy, specifically by electron microscope image analysis. Specifically, the liquid crystal sealant is subjected to image analysis, 50 organic fillers having a particle diameter of 4 ⁇ m or more are selected, and the average value when the particle diameter is measured is defined as the average particle diameter of the organic filler A. Similarly, the liquid crystal sealant is subjected to image analysis, 50 organic fillers having a particle size of 1 ⁇ m or less are selected, and the average value when the particle size is measured is defined as the average particle size of the organic filler B.
- the organic filler A deforms reversibly or irreversibly, thereby suppressing liquid crystal leakage.
- the gap between the organic fillers A is filled with the organic filler B, and the linearity in the line width direction of the seal pattern of the liquid crystal sealant is increased.
- the organic filler B increases the stress relaxation property of the sealing member and increases the adhesive strength between the sealing member and the substrate.
- W1 / (W1 + W2) is 0.25 to 0.75, preferably 0.3 to It is 0.7, more preferably 0.4 to 0.6.
- W1 / (W1 + W2) is 0.25 to 0.75, preferably 0.3 to It is 0.7, more preferably 0.4 to 0.6.
- the viscosity of the liquid crystal sealing agent is excessively increased, the thixotropy is lowered, and bubbles are easily caught during the preparation of the liquid crystal sealing agent. If it is within the range, the viscosity of the liquid crystal sealant tends to fall within an appropriate range.
- Examples of methods for measuring the ratio of the mass W1 of the organic filler A and the mass W2 of the organic filler B contained in the liquid crystal sealant include the following methods.
- a cured film having a certain thickness is prepared using a liquid crystal sealant, and the cured film is observed with a TEM (transmission electron microscope). Then, the particle diameter and number of organic fillers present in a certain volume are analyzed.
- the observed organic filler is divided into an organic filler A having a particle size of 4 ⁇ m or more and an organic filler B having a particle size of 1 ⁇ m or less.
- the volume of the organic filler calculated from each particle size, From the specific gravity, the mass W1 of the organic filler A and the mass content W2 of the organic filler B contained in the liquid crystal sealant are calculated.
- the total amount of the organic filler A and the organic filler B contained in the liquid crystal sealant is the total (resin unit) of the aforementioned (1a) (meth) acrylic resin and (1b) (meth) acryl-modified epoxy resin (100 mass).
- the amount is preferably 20 to 100 parts by mass, more preferably 20 to 80 parts by mass, and still more preferably 20 to 60 parts by mass with respect to parts. If the total amount of the organic filler A and the organic filler B is 20 parts by mass or more, the effect of adding the organic filler is easily obtained. On the other hand, when the amount of the organic filler A and the organic filler B is 100 parts by mass or less, the filler A and the filler B are easily sufficiently bound by the resin component described above.
- the amount of the organic filler A contained in the liquid crystal sealant is 5 with respect to 100 parts by mass of the total (resin unit) of the above-mentioned (1a) (meth) acrylic resin and (1b) (meth) acrylic-modified epoxy resin. It is preferably ⁇ 75 parts by mass, more preferably 6 to 70 parts by mass, still more preferably 6 to 60 parts by mass, and particularly preferably 6 to 40 parts by mass. Further, the amount of the organic filler B contained in the liquid crystal sealant is also 5 with respect to 100 parts by mass of the total (resin unit) of the aforementioned (1a) (meth) acrylic resin and (1b) (meth) acrylic-modified epoxy resin. It is preferably ⁇ 75 parts by mass, more preferably 6 to 70 parts by mass, still more preferably 6 to 60 parts by mass, and particularly preferably 6 to 40 parts by mass.
- the organic filler A and the organic filler B are difficult to melt at the thermosetting temperature of the liquid crystal sealant.
- the softening point of the organic filler A and the organic filler B is preferably 30 to 120 ° C.
- the organic filler A easily deforms at the temperature, and the organic filler A easily deforms between the two substrates to fill these gaps. It becomes easy.
- the softening point of the organic filler B is in the above range, the organic filler B easily enters a gap between the organic fillers A, and the line width of the seal pattern is likely to be uniform.
- organic filler A and the organic filler B include fine particles selected from the group consisting of silicone fine particles, acrylic fine particles, styrene fine particles such as styrene / divinylbenzene copolymer, and polyolefin fine particles.
- the shapes of the organic filler A and the organic filler B are not particularly limited, but are preferably spherical and more preferably spherical.
- the particle size of the filler can be measured by microscopy, specifically by image analysis with an electron microscope.
- the surface of the organic filler A and the organic filler B is smooth. If the surface is smooth, the specific surface area decreases, and the amount of organic filler A and organic filler B that can be added to the liquid crystal sealant increases.
- the organic filler A and the organic filler B are preferably spherical in a liquid crystal sealing agent or have a smooth surface, but spherical in a sealing member (cured product of a liquid crystal sealing agent) in a liquid crystal display panel. Even if not, it does not have to have a smooth surface. This is because the organic filler in the liquid crystal sealant is deformed during the manufacturing process of the liquid crystal display panel.
- the liquid crystal sealant may contain organic particles having an average particle diameter of more than 1 ⁇ m and less than 5 ⁇ m as long as the effects of the present invention are not impaired.
- radical photopolymerization initiators can be used.
- radical photopolymerization initiators include alkylphenone compounds, acyl phosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, ⁇ -acyro
- examples include oxime ester compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, anthraquinone compounds, and the like.
- alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651); 2-methyl-2-morpholino (4-thiomethylphenyl) propane ⁇ -aminoalkylphenones such as 1-one (IRGACURE 907); ⁇ -hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184) and the like.
- the acyl phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- the titanocene-based compound includes bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like.
- Examples of the oxime ester compound include 1.2-octanedione-1- [4- (phenylthio) -2- (0-benzoyloxime)] (IRGACURE OXE 01) and the like.
- thermal radical polymerization initiators examples include organic peroxide compounds and azo compounds.
- thermal radical polymerization initiator those having a lower limit of 10 hours half-life temperature of 80 ° C. and an upper limit of 150 ° C. are preferably used.
- organic peroxide compounds include ketone peroxide compounds such as methyl ethyl ketone peroxide; peroxyketal compounds such as 1,1-di (t-butyloxy) cyclohexane; t-butyl peroxybivalate, etc.
- Alkyl peroxyester compounds such as diacyl peroxide compounds such as dilauroyl peroxide; peroxydicarbonate compounds such as (2-ethylhexyl) peroxydicarbonate; peroxycarbonates such as t-butylperoxyisopropyl carbonate
- a dialkyl peroxide compound such as di-t-butyl peroxide; a hydroperoxide compound such as t-amyl hydroperoxide; and the like.
- azo compound examples include 1,1′-azobis (2,4-cyclohexane) -1-carbonitrile, 2,2′-azobis [(2-imidazoline-2-el) propane] disulfate dihydride.
- Water-soluble azo compounds such as late; oil-soluble azo compounds such as 1-[(cyano-1-methyl) azo] formamide; polymer azo compounds; and the like.
- the content of the radical polymerization initiator in the liquid crystal sealant is 0.01 to 100 parts by mass with respect to 100 parts by mass of the resin unit that is the total of (1a) (meth) acrylic resin and (1b) (meth) acrylic-modified epoxy resin. It is preferably 3.0 parts by mass.
- the content of the radical polymerization initiator is 0.01 parts by mass or more, the curability of the liquid crystal sealant is improved.
- the content is 3.0 parts by mass or less, the stability during application to the substrate is improved.
- the liquid crystal sealing agent may include an epoxy curing agent.
- the epoxy curing agent referred to in the present invention does not cure the epoxy resin in a state where the resin is normally stored (room temperature, under visible light, etc.) even when mixed with the epoxy resin, but cures the epoxy resin when given heat. It is a curing agent.
- a liquid crystal sealant containing an epoxy curing agent is excellent in storage stability and thermosetting.
- the epoxy curing agent may be a known one, but it has a melting point of 50 ° C. or more and 250 ° C. or less from the viewpoint of enhancing the viscosity stability of the liquid crystal sealant and maintaining the moisture resistance, depending on the thermosetting temperature.
- An epoxy curing agent is preferable, an epoxy curing agent having a melting point of 100 ° C. or higher and 200 ° C. or lower is more preferable, and an epoxy curing agent having a melting point of 150 ° C. or higher and 200 ° C. or lower is further preferable.
- Preferred examples of such an epoxy curing agent include organic acid dihydrazide compounds, imidazole compounds, dicyandiamide compounds, and polyamine compounds.
- organic acid dihydrazide compounds include adipic acid dihydrazide (melting point 181 ° C.), 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (melting point 120 ° C.), 7,11-octadecadien-1 , 18-dicarbohydrazide (melting point 160 ° C.), dodecanedioic acid dihydrazide (melting point 190 ° C.), sebacic acid dihydrazide (melting point 189 ° C.), and the like.
- imidazole compounds include 2,4-diamino-6- [2′-ethylimidazolyl- (1 ′)]-ethyltriazine (melting point 215 to 225 ° C.) and 2-phenylimidazole (melting point 137 to 147 ° C. ) Etc. are included.
- Examples of the dicyandiamide compound include dicyandiamide (melting point: 209 ° C.).
- the polyamine-based compound is a thermal latent curing agent having a polymer structure obtained by reacting an amine and an epoxy.
- the liquid crystal sealing agent may contain only one kind or two or more kinds.
- the content of the epoxy curing agent in the liquid crystal sealant is 3 to 30 parts by mass with respect to 100 parts by mass of the resin unit which is the total of (1a) (meth) acrylic resin and (1b) (meth) acrylic modified epoxy resin. It is preferable that
- the liquid crystal sealing agent containing an epoxy curing agent can be a so-called one-part curable resin composition.
- the one-component curable resin composition is excellent in workability because it is not necessary to mix the main agent and the curing agent when used.
- the liquid crystal sealing agent of the present invention may further contain an inorganic filler.
- an inorganic filler By adding the inorganic filler, it is possible to control the viscosity of the liquid crystal sealant, the strength of the cured product, the linear expansion, and the like.
- the inorganic filler is not particularly limited, but examples thereof include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, Inorganic fillers such as potassium titanate, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride are included, and silicon dioxide and talc are preferable.
- the shape of the inorganic filler is not particularly limited, and may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or an irregular shape.
- the inorganic filler preferably has an average primary particle size of 1.5 ⁇ m or less and a specific surface area of 0.5 m 2 / g to 20 m 2 / g.
- the average primary particle diameter of the inorganic filler can be measured by a laser diffraction method described in JIS Z8825-1.
- the specific surface area can be measured by the BET method described in JIS Z8830.
- the content of the inorganic filler in the liquid crystal sealant is 3 to 30 parts by mass with respect to 100 parts by mass of the resin unit which is the total of (1a) (meth) acrylic resin and (1b) (meth) acrylic modified epoxy resin. Preferably there is.
- Epoxy resin The liquid crystal sealant may contain an epoxy resin. Epoxy resin has low solubility and diffusibility in liquid crystal, and not only good display characteristics of the obtained liquid crystal panel, but also can improve the moisture resistance of the cured product.
- Such an epoxy resin may be an aromatic epoxy resin having a weight average molecular weight of 500 to 10,000, preferably 1000 to 5,000.
- the weight average molecular weight of the epoxy resin can be measured (polystyrene conversion) by, for example, gel permeation chromatography (GPC).
- aromatic epoxy resins examples include aromatic diols represented by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, and the like, diols obtained by modifying these with ethylene glycol, propylene glycol, and alkylene glycol, Aromatic polyvalent glycidyl ether compound obtained by reaction with epichlorohydrin; reaction of epichlorohydrin with polyphenols such as novolak resins derived from phenol or cresol and formaldehyde, polyalkenylphenol and copolymers thereof, etc. The obtained novolak type polyvalent glycidyl ether compound; glycidyl ether compounds of xylylene phenol resin, and the like are included.
- the above aromatic epoxy resins include, among others, cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, triphenolmethane type epoxy resins, triphenolethane type epoxy resins, trisphenol type epoxy resins.
- Resin, dicyclopentadiene type epoxy resin, diphenyl ether type epoxy resin, and biphenyl type epoxy resin are preferable. Furthermore, you may mix and use these.
- the content of the epoxy resin is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the resin unit that is the total of the (1a) (meth) acrylic resin and the (1b) (meth) acrylic-modified epoxy resin. . If the epoxy resin content is too high, the viscosity of the liquid crystal sealant will increase and the applicability may decrease. If the epoxy resin content is too low, the liquid crystal sealant will not have sufficient moisture resistance. It may become.
- the epoxy resin may be liquid or solid. In the case of a solid epoxy resin, the softening point is preferably 40 ° C or higher and 150 ° C or lower.
- the liquid crystal sealing agent may contain a light shielding agent for the purpose of imparting a function as a light shielding part to the sealing member.
- the sealing member functions as a light shielding portion of the liquid crystal panel.
- the light shielding agent can be, for example, a black pigment or a black dye. Examples of these include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and organic pigments.
- the shape of the light shielding agent is not particularly limited, and may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or an irregular shape.
- the light shielding agent preferably has an average primary particle size of 1.0 ⁇ m or less.
- the average primary particle diameter of the inorganic filler can be measured by a laser diffraction method described in JIS Z8825-1.
- the content of the light-shielding agent is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the resin unit which is the total of (1a) (meth) acrylic resin and (1b) (meth) acrylic-modified epoxy resin. .
- the viscosity of a liquid-crystal sealing compound will become high and applicability
- paintability may fall. If the amount of the light shielding agent is too small, the light shielding property of the seal member may be insufficient.
- liquid crystal sealants for liquid crystal sealants, as necessary, coupling agents such as thermal radical polymerization initiators, silane coupling agents, ion trapping agents, ion exchange agents, leveling agents, pigments, dyes, plasticizers In addition, additives such as an antifoaming agent may be further included. In addition, a spacer or the like may be blended to adjust the gap of the liquid crystal panel.
- coupling agents such as thermal radical polymerization initiators, silane coupling agents, ion trapping agents, ion exchange agents, leveling agents, pigments, dyes, plasticizers
- additives such as an antifoaming agent may be further included.
- a spacer or the like may be blended to adjust the gap of the liquid crystal panel.
- the viscosity at 25 ° C. and 2.5 rpm of the E-type viscometer of the liquid crystal sealant of the present invention is preferably 200 to 450 Pa ⁇ s, and more preferably 300 to 400 Pa ⁇ s.
- the viscosity is in the above range, the liquid crystal sealing agent is likely to be deformed into a predetermined shape when the substrates of the liquid crystal cell are overlapped. Therefore, the gap width between the substrates of the liquid crystal cell can be controlled appropriately.
- the thixotropy index (TI value) of the liquid crystal sealant of the present invention is preferably 1.0 to 1.5, more preferably 1.1 to 1.3 from the viewpoint of applicability of the liquid crystal sealant. It is.
- the TI value was determined by measuring the viscosity ⁇ 1 of the liquid crystal sealant at room temperature (25 ° C.) and 0.5 rpm using the E-type viscometer, and the viscosity ⁇ 2 of the liquid crystal sealant at 5 rpm. ) Is a value obtained by applying to.
- TI value (viscosity ⁇ 1 at 0.5 rpm (25 ° C.)) / (Viscosity ⁇ 2 at 5 rpm (25 ° C.)) (1)
- the liquid crystal sealant of the present invention is preferably used for a liquid crystal sealant for a liquid crystal dropping method in which photocuring and heat curing are often used in combination.
- a liquid crystal display panel produced by the method of the present invention includes a display substrate, a counter substrate paired therewith, a frame-shaped sealing member interposed between the display substrate and the counter substrate, And a liquid crystal layer filled in a space surrounded by a seal member between the display substrate and the counter substrate.
- the cured product of the liquid crystal sealant is used as a seal member.
- the display substrate and the counter substrate are both transparent substrates.
- the material of the transparent substrate can be glass or plastic such as polycarbonate, polyethylene terephthalate, polyethersulfone and PMMA.
- a matrix-like TFT, a color filter, a black matrix or the like can be arranged on the surface of the display substrate or the counter substrate.
- An alignment film is further formed on the surface of the display substrate or the counter substrate.
- the alignment film contains a known organic alignment agent, inorganic alignment agent, and the like.
- Such a liquid crystal display panel is manufactured using the liquid crystal sealant of the present invention.
- a liquid crystal dropping method and a liquid crystal injecting method as a method for manufacturing a liquid crystal display panel, but the method for manufacturing a liquid crystal display panel of the present invention is preferably a liquid crystal dropping method.
- the manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is a1) a first step of forming a seal pattern of the liquid crystal sealant of the present invention on one substrate; a2) a second step of dropping the liquid crystal in a region surrounded by the seal pattern of the substrate or a region of the other substrate facing the region surrounded by the seal pattern in a state where the seal pattern is uncured; a3) a third step of superimposing one substrate and the other substrate via a seal pattern; a4) a fourth step of curing the seal pattern.
- the state in which the seal pattern is uncured in step a2) means a state in which the curing reaction of the liquid crystal sealant has not progressed to the gel point. For this reason, in step a2), the seal pattern may be semi-cured by light irradiation or heating in order to suppress dissolution of the liquid crystal sealant in the liquid crystal.
- One substrate and the other substrate are a display substrate or a counter substrate, respectively.
- the organic filler A having a relatively large average particle size contained in the liquid crystal sealant is reversibly or irreversibly deformed.
- Deformation means being crushed or crouched. That is, the organic filler A in the liquid crystal sealant is preferably spherical; however, the organic filler A in the liquid crystal seal of the liquid crystal display panel does not need to be spherical and is crushed.
- the liquid crystal sealant of the present invention contains the organic filler B having a relatively small average particle diameter, the liquid crystal sealant is easily applied evenly even if the width of the seal pattern is narrowed.
- the line width of the seal pattern is preferably 0.2 to 1.0 mm, more preferably 0.2 to 0.7 mm.
- the liquid crystal sealing agent of the present invention when used as a sealing member, the organic filler A is crushed and the liquid crystal leakage is effectively suppressed. Moreover, the adhesive strength between the substrates increases. On the other hand, since the liquid crystal sealant contains the organic filler B having a relatively small average particle diameter, even if the width of the seal member is thin, the line width is likely to be uniform, and a portion with low local strength is unlikely to occur. .
- the ratio of the organic filler A and the organic filler B contained in the liquid crystal sealant is within a predetermined range, the viscosity of the liquid crystal sealant is moderately low. Therefore, when the substrates of the liquid crystal cell are overlapped, it is easy to appropriately control the gap width between the substrates.
- step a4) only curing by heating may be performed, but curing by light irradiation (temporary curing) may be performed, followed by curing by heating (main curing). Dissolution in the liquid crystal can be suppressed by instantaneously curing the liquid crystal sealant by temporary curing by light irradiation.
- the light irradiation time is, for example, about 10 minutes, although it depends on the composition of the liquid crystal sealant.
- the light irradiation energy may be energy that can cure (meth) acrylic resin, (meth) acryl-modified epoxy resin, and the like.
- the light is preferably ultraviolet light.
- the thermosetting temperature is 120 ° C., for example, although it depends on the composition of the liquid crystal sealant, and the thermosetting time is about 2 hours.
- the liquid crystal display panel of the present invention provides a high quality display device because liquid crystal leakage is suppressed and the adhesive strength between the substrate and the sealing member is high.
- Resin 1a Bifunctional acrylic resin: Bisphenol A type epoxy resin-modified diacrylate (3002A, manufactured by Kyoeisha Chemical Co., Ltd., hydrogen bonding functional group equivalent 3.3 ⁇ 10 ⁇ 3
- Acrylic modified epoxy resin An acrylic-modified epoxy resin prepared by the following method was used. (Preparation method) A 500 mL four-necked flask equipped with a stirrer, gas introduction tube, thermometer, and cooling tube is charged with 160 g of bisphenol F type epoxy resin (EXA-835LV DIC), 36 g of acrylic acid, and 0.2 g of triethanolamine and dried. Under an air stream, the mixture was heated and stirred at 110 ° C. for 5 hours to obtain an acrylic-modified epoxy resin. The obtained acrylic-modified epoxy resin was washed 12 times with ultrapure water. The hydrogen-bonding functional group equivalent of the acrylic-modified epoxy resin was 2.1 ⁇ 10 ⁇ 3 .
- Organic filler A (2-1) GBM-55S (crosslinked polybutyl acrylate-methyl methacrylate graft copolymer, manufactured by Aika Industries, average particle size 6 ⁇ m) (2-2) P-800T (urethane powder, manufactured by Negami Kogyo Co., Ltd., average particle size 7 ⁇ m) (2-3) KMP600 (silicone rubber powder, manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 5 ⁇ m) (2-4) SE-006T (acrylic powder, manufactured by Negami Kogyo Co., Ltd., average particle size 6 ⁇ m)
- Organic filler B F351 (alkyl methacrylate copolymer, manufactured by Aika Industry Co., Ltd., average particle size 0.3 ⁇ m)
- Epoxy resin Epicron 850CRP (Bisphenol A type epoxy resin: manufactured by DIC)
- Epoxy curing agent thermo latent curing agent: 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (Amicure VHD manufactured by Ajinomoto Co., Inc.)
- Additive ⁇ -glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
- Example 1 70 parts by weight of bifunctional acrylic resin, 15 parts by weight of organic filler A (2-1), 5 parts by weight of organic filler B, 1 part by weight of thermal radical polymerization initiator (4-1), 5 parts by weight of epoxy resin 3 parts by mass of a heat latent curing agent and 1 part by mass of an additive are mixed thoroughly using a three roll so that the liquid composition is uniform, Obtained.
- Viscosity The viscosity of the obtained liquid crystal sealant was measured with an E-type viscometer at 25 ° C. at 1.0 rpm and 2.5 rpm.
- TI value Thixotropic index (TI value) Using an E-type viscometer, the viscosity ⁇ 1 of the liquid crystal sealant at room temperature (25 ° C.) and 0.5 rpm, and the viscosity ⁇ 2 of the liquid crystal sealant at 5 rpm were measured. These measured values were applied to the following formula (1) to obtain a TI value.
- TI value (viscosity ⁇ 1 at 0.5 rpm (25 ° C.)) / (Viscosity ⁇ 2 at 5 rpm (25 ° C.)) (1)
- Adhesive strength A liquid crystal sealant was printed on a non-alkali glass having a size of 25 mm ⁇ 45 mm ⁇ thickness 5 mm using a screen plate.
- the seal pattern was circular with a diameter of 1 mm. And it mounted in the alkali-free glass used as a pair in the seal pattern shape, and was fixed with the jig
- the test piece fixed with the jig was irradiated with 100 mW / cm 2 of ultraviolet rays from an ultraviolet irradiation device (USHIO INC.), The liquid crystal sealant was cured. At this time, the illuminance energy of ultraviolet rays was set to 2000 mJ / cm 2 .
- the test piece in which the liquid crystal sealant was cured by light was heat-treated at 120 ° C. for 60 minutes using an oven to obtain a sample for measuring the adhesive strength.
- the tensile rate was 2 mm / min, and the cured liquid crystal sealant was peeled off in a direction parallel to the glass bottom surface, thereby measuring the plane tensile strength.
- the adhesive strength was evaluated as follows in four stages according to the magnitude of the plane tensile strength.
- ⁇ Tensile strength is 20 MPa or more and less than 25 MPa, adhesive strength.
- X Tensile strength is less than 20 MPa, and adhesive strength is low
- a liquid crystal material (MLC-11900-000: Merck) corresponding to the panel internal volume after bonding was precisely dropped into the seal pattern of the substrate with a dispenser (manufactured by Hitachi Plant Technology). And with the vacuum bonding apparatus (made by Shin-Etsu Engineering Co., Ltd.), the above-mentioned glass substrate and the glass substrate which opposes were piled up under reduced pressure of 10 Pa * s, and it fixed with the load.
- the sample after fixation was irradiated with 100 mW / cm 2 of ultraviolet light from an ultraviolet irradiation device (USHIO INC.) To cure the liquid crystal sealant. At this time, the illuminance energy of ultraviolet rays was set to 2000 mJ / cm 2 . After the liquid crystal sealant was cured by light, a liquid crystal display panel was produced by heat treatment at 120 ° C. for 60 minutes using an oven.
- an ultraviolet irradiation device USHIO INC.
- Leak resistance 1 part by mass of a 5 ⁇ m spherical spacer was further added to the liquid crystal sealants of the examples and comparative examples.
- the obtained composition is filled in a dispenser (manufactured by Hitachi Plant Technology Co., Ltd.) and is formed into a rectangular frame shape of 35 mm ⁇ 40 mm and a line width of 0.7 mm on a 40 mm ⁇ 50 mm ⁇ 0.7 mm thick alkali-free glass substrate.
- the seal pattern was drawn with a cross-sectional area of 3500 ⁇ m 2 .
- a liquid crystal material (MLC-11900-000: Merck) corresponding to the panel internal volume after bonding was precisely dropped into the seal pattern of the substrate with a dispenser (manufactured by Hitachi Plant Technology).
- a dispenser manufactured by Hitachi Plant Technology
- the above glass substrate and the glass substrate facing each other were superposed under a reduced pressure of 10 Pa ⁇ s, and fixed under a load.
- a liquid crystal material (MLC-11900-000: Merck) corresponding to the panel internal volume after bonding was precisely dropped into the seal pattern of the substrate with a dispenser (manufactured by Hitachi Plant Technology).
- a dispenser manufactured by Hitachi Plant Technology
- the above glass substrate and the glass substrate facing each other were superposed under a reduced pressure of 10 Pa ⁇ s, and fixed under a load.
- the fixed sample was irradiated with 100 mW / cm 2 of ultraviolet light from an ultraviolet irradiation device (USHIO INC.) To cure the liquid crystal sealant. At this time, the illuminance energy of ultraviolet rays was set to 2000 mJ / cm 2 . After the liquid crystal sealant was cured by light, it was heat-treated at 120 ° C. for 60 minutes using an oven to produce a liquid crystal display panel. On the other hand, in Examples 1 to 5, 8 to 14, and Comparative Examples 1 to 3 and 6 to 9, the fixed samples were heat-treated at 120 ° C. for 60 minutes using an oven to prepare liquid crystal display panels.
- wire width of the sealing member was measured with the optical microscope.
- the uniformity of the line width was evaluated as follows. ⁇ : When either or both of the maximum and minimum values of the line width are not within the range of ⁇ 20% of the average value of the line width ⁇ : Both the maximum and minimum values of the line width are When the average value is within ⁇ 20%, but either one or both are ⁇ 10% or more of the average value of the line width ⁇ : Both the maximum value and the minimum value of the line width are average values of the line width When it is within the range of less than ⁇ 10% of the value
- Tables 1 and 2 summarize the compositions and evaluation results of the liquid crystal sealants of the examples and comparative examples.
- the panel gap control is also assumed to be low for the same reason. Furthermore, when the inorganic filler which has the same metal particle diameter was included instead of the organic filler B (Comparative Example 8), the adhesive strength was low and the leak resistance was low. Since the inorganic filler is harder than the organic filler B, it is presumed that the seal pattern hardly adheres to the substrate and it is difficult to sufficiently increase the adhesive strength.
- the present invention relates to a liquid crystal sealant capable of forming a seal member that suppresses leakage of liquid crystal and has high adhesive strength between the seal member and the substrate even if the seal pattern is thinned.
- a liquid crystal display device is provided.
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Abstract
Description
[1](1a)(メタ)アクリル樹脂、または(1b)分子内にエポキシ基及び(メタ)アクリル基を有する(メタ)アクリル変性エポキシ樹脂と、(2)平均粒子径4~13μmの有機フィラーAと、(3)平均粒子径0.05~1μmの有機フィラーBと、(4)ラジカル重合開始剤と、を含み、前記成分(2)の含有量(質量)をW1とし、前記成分(3)の含有量(質量)をW2とするとき、0.25≦W1/(W1+W2)≦0.75である、液晶シール剤。
0.4≦W1/(W1+W2)≦0.6
[3]前記成分(1a)および前記成分(1b)を合わせた樹脂ユニット100質量部に対して、前記成分(2)及び前記成分(3)の合計量が、20~100質量部である、[1]または[2]に記載の液晶シール剤。
[4]前記成分(2)及び前記成分(3)はそれぞれ、シリコーン微粒子、アクリル微粒子、スチレン微粒子、およびポリオレフィン微粒子からなる群より選ばれる一種類以上の微粒子である、[1]~[3]のいずれかに記載の液晶シール剤。
[5]前記成分(1a)及び前記成分(1b)を合わせた樹脂ユニット100質量部に対して、前記成分(4)の含有量が、0.01~3.0質量部である、[1]~[4]のいずれかに記載の液晶シール剤。
[7](6)無機フィラーをさらに含み、前記成分(1a)および前記(1b)を合わせた樹脂ユニット100質量部に対して、前記成分(6)の含有量が、3~30質量部である、[1]~[6]のいずれかに記載の液晶シール剤。
[8](7)遮光剤をさらに含み、前記(1a)および前記(1b)を合わせた樹脂ユニット100質量部に対して、前記成分(7)の含有量が3~30質量部である、[1]~[7]のいずれかに記載の液晶シール剤。
[9]E型粘度計で測定される、25℃、2.5rpmにおける粘度が200~450Pa・sである、[1]~[8]のいずれかに記載の液晶シール剤。
[10]液晶滴下工法による液晶表示パネルの製造に用いられる、[1]~[9]のいずれかに記載の液晶シール剤。
[11]前記[1]~[9]のいずれかに記載の液晶シール剤を用いて、一方の基板にシールパターンを形成する工程と、前記シールパターンが未硬化の状態において、前記一方の基板のシールパターン領域内、または前記一方の基板と対になる他方の基板に液晶を滴下する工程と、前記一方の基板と、前記他方の基板とを重ね合わせる工程と、前記シールパターンを硬化させる工程と、を含む液晶表示パネルの製造方法。
本発明の液晶シール剤には、(1)樹脂と、(2)平均粒子径の異なる2種類の有機フィラーと、(3)ラジカル重合開始剤と、が含まれる。また、液晶シール剤には必要に応じて(4)エポキシ硬化剤や、(5)無機フィラー、(6)エポキシ樹脂、(7)遮光剤等が含まれてもよい。
液晶シール剤には、(1a)(メタ)アクリル樹脂、または(1b)1分子内にエポキシ基と(メタ)アクリル基とを有する(メタ)アクリル変性エポキシ樹脂が少なくとも含まれる。これらは1種のみ含まれてもよく、2種以上が含まれてもよい。液晶シール剤に、(1b)(メタ)アクリル変性エポキシ樹脂が含まれると、液晶シール剤の硬化物(シール部材)の耐湿性が高まる。
液晶シール剤には、平均粒子径4~13μmの有機フィラーAと、平均粒子径0.05~1μmの有機フィラーBとが含まれる。有機フィラーAの平均粒子径は好ましくは4~10μmであり、さらに好ましくは5~8μmである。一方、有機フィラーBの平均粒子径は、好ましくは0.1~0.8μmであり、さらに好ましくは0.1~0.6μmである。
液晶シール剤には、(1a)(メタ)アクリル樹脂や(1b)(メタ)アクリル変性エポキシ樹脂等を光硬化反応させるための光ラジカル重合開始剤や熱硬化反応させるための熱ラジカ重合開始剤が含まれる。
前述のように、液晶シール剤には、エポキシ硬化剤が含まれてもよい。本発明でいうエポキシ硬化剤とは、エポキシ樹脂に混合されていても、樹脂を通常保存する状態(室温、可視光線下等)ではエポキシ樹脂を硬化させないが、熱を与えられるとエポキシ樹脂を硬化させる硬化剤である。エポキシ硬化剤を含有する液晶シール剤は、保存安定性に優れ、かつ熱硬化性に優れる。
本発明の液晶シール剤には、さらに無機フィラーが含まれてもよい。無機フィラーの添加により、液晶シール剤の粘度、硬化物の強度、および線膨張性の制御等を行うことができる。
液晶シール剤には、エポキシ樹脂が含まれてもよい。エポキシ樹脂は、液晶に対する溶解性、拡散性が低く、得られる液晶パネルの表示特性が良好であるだけでなく、硬化物の耐湿性を高めうる。
液晶シール剤には、シール部材に遮光部としての機能を付与する目的で、遮光剤が含まれてもよい。液晶シール剤に遮光剤が含まれると、シール部材が液晶パネルの遮光部として機能する。遮光剤は、例えば黒色顔料や黒色染料等でありうる。これらの例には、カーボンブラック、酸化クロム、酸化鉄、チタンブラック、アニリンブラック、有機系顔料等が含まれる。
液晶シール剤には、必要に応じて熱ラジカル重合開始剤、シランカップリング剤等のカップリング剤、イオントラップ剤、イオン交換剤、レベリング剤、顔料、染料、可塑剤、消泡剤等の添加剤がさらに含まれてもよい。また、液晶パネルのギャップを調整するためにスペーサー等が配合されていてもよい。
TI値=(0.5rpmにおける粘度η1(25℃))/(5rpmにおける粘度η2(25℃))・・・(1)
本発明の方法で作製する液晶表示パネルは、表示基板と、それと対になる対向基板と、表示基板と対向基板との間に介在している枠状のシール部材と、表示基板と対向基板との間のシール部材で囲まれた空間に充填された液晶層とを含む。本発明の方法では、前述の液晶シール剤の硬化物を、シール部材とする。
a1)一方の基板に、本発明の液晶シール剤のシールパターンを形成する第1の工程と、
a2)シールパターンが未硬化の状態において、基板のシールパターンで囲まれた領域内、またはシールパターンで囲まれた領域に対向する他方の基板の領域に、液晶を滴下する第2の工程と、
a3)一方の基板と、他方の基板とを、シールパターンを介して重ね合わせる第3の工程と、
a4)シールパターンを硬化させる第4の工程と、を含む。
(1)樹脂
(1a)2官能アクリル樹脂:
ビスフェノールA型エポキシ樹脂変性ジアクリレート(3002A、共栄社化学株式会社製、水素結合性官能基当量3.3×10-3)
(1b)アクリル変性エポキシ樹脂:
以下の方法で調製されるアクリル変性エポキシ樹脂とした。(調製方法)
攪拌機、気体導入管、温度計、冷却管を備えた500mLの四つ口フラスコにビスフェノールF型エポキシ樹脂(EXA-835LV DIC社製)160g、アクリル酸36g、トリエタノールアミン0.2gを仕込み、乾燥エア気流下、110℃、5時間加熱攪拌してアクリル変性エポキシ樹脂を得た。得られたアクリル変性エポキシ樹脂を超純水にて12回洗浄した。アクリル変性エポキシ樹脂の水素結合性官能基当量は2.1×10-3であった。
(2-1)GBM-55S(架橋ポリアクリル酸ブチル-メタクリル酸メチルグラフト共重合体、アイカ工業社製、平均粒子径6μm)
(2-2)P-800T(ウレタンパウダー、根上工業社製、平均粒子径7μm)
(2-3)KMP600(シリコーンゴムパウダー、信越化学工業(株)製、平均粒子径5μm)
(2-4)SE-006T(アクリルパウダー、根上工業社製、平均粒子径6μm)
F351(メタクリル酸アルキル共重合体、アイカ工業社製、平均粒子径0.3μm)
(4-1)熱ラジカル重合開始剤:1,1’-アゾビス(2,4-シクロヘキサン-1-カルボニトリル(V-40:和光純薬工業株式会社製)
(4-2)光ラジカル重合開始剤:2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(IRGACURE 651: BASF社製)
無機フィラー:KE-S30(球状シリカ、日本触媒社製、平均粒子径0.24μm、最大粒子径0.9μm)
エポキシ樹脂:エピクロン850CRP(ビスフェノールA型エポキシ樹脂:DIC社製)
エポキシ硬化剤(熱潜在性硬化剤): 1,3-ビス(ヒドラジノカルボエチル)-5-イソプロピルヒダントイン(アミキュアVHD 味の素社製)
添加剤:γ-グリシドキシプロピルトリメトキシシラン(KBM-403、信越化学工業社製)
2官能アクリル樹脂を70質量部、有機フィラーA(2-1)を15質量部、有機フィラーBを5質量部、熱ラジカル重合開始剤(4-1)を1質量部、エポキシ樹脂を5質量部、熱潜在性硬化剤を3質量部、添加剤を1質量部、を含む樹脂組成物を、三本ロールを用いて液組成が均一になるように十分に混合して、液晶シール剤を得た。
表1及び表2に記載の組成(質量比)で、実施例1と同様に液晶シール剤を得た。
各実施例および比較例で得られた液晶シール剤について、以下の項目を評価した。
得られた液晶シール剤の粘度を、E型粘度計により25℃で、1.0rpm及び2.5rpmにて測定した。
E型粘度計を用い、室温(25℃)、0.5rpmにおける液晶シール剤の粘度η1、5rpmにおける液晶シール剤の粘度η2を測定した。これらの測定値を、下記式(1)に当てはめてTI値を求めた。
TI値=(0.5rpmにおける粘度η1(25℃))/(5rpmにおける粘度η2(25℃))・・・(1)
スクリーン版を使用して液晶シール剤を25mm×45mm×厚さ5mmの無アルカリガラス上に印刷した。シールパターンは、直径1mmの円状とした。そして、対となる無アルカリガラスにシールパターン状に載置し、治具で固定した。
◎:引張強度が30MPa以上であり、接着強度が非常に良好である
〇:引張強度が25MPa以上30MPa未満であり、接着強度が良好である
△:引張強度が20MPa以上25MPa未満であり、接着強度が良好である
×:引張強度が20MPa未満であり、接着強度が低い
各実施例および比較例の液晶シール剤に、5μmの球状スペーサーを1質量部さらに添加した。得られた組成物をディスペンサー(日立プラントテクノロジー社製)に充填し、40mm×50mm×厚さ0.7mmの無アルカリガラスの基板の上に35mm×40mm、線幅0.7mmの四角形の枠状のシールパターンを断面積3500μm2で描画した。当該基板のシールパターン内に、貼り合せ後のパネル内容量に相当する液晶材料(MLC-11900-000:メルク社)をディスペンサー(日立プラントテクノロジー社製)にて精密に滴下した。そして真空貼り合せ装置(信越エンジニアリング社製)にて、10Pa・sの減圧下で前述のガラス基板と対向するガラス基板とを重ね合わせ、荷重をかけて固定した。
×:ギャップの最大値、最小値のいずれか一方もしくは両方が、5μm±0.2μmの範囲に無い場合
△:ギャップの最大値、最小値の両方が5μm±0.20μmの範囲内にあるものの、少なくとも一方、もしくは両方が5μm±0.15μmの範囲内に無い場合
〇:ギャップの最大値、最小値の両方が、5μm±0.15μmの範囲内にあるものの、少なくとも一方、もしくは両方が5μm±0.10μmの範囲内に無い場合
◎:ギャップの最大値、最小値の両方が5μm±0.10μmの範囲内に有る場合
各実施例および比較例の液晶シール剤に、5μmの球状スペーサーを1質量部さらに添加した。得られた組成物をディスペンサー(日立プラントテクノロジー社製)に充填し、40mm×50mm×厚さ0.7mmの無アルカリガラスの基板の上に35mm×40mm、線幅0.7mmの四角形の枠状のシールパターンを断面積3500μm2で描画した。当該基板のシールパターン内に、貼り合せ後のパネル内容量に相当する液晶材料(MLC-11900-000:メルク社)をディスペンサー(日立プラントテクノロジー社製)にて精密に滴下した。真空貼り合せ装置(信越エンジニアリング社製)にて、10Pa・sの減圧下で前述のガラス基板と対向するガラス基板とを重ね合わせ、荷重をかけ固定した。
◎:大気圧解放後、10分以上放置しても液晶は漏出せず、更にシール剤への液晶の入り込みが観察されなかった
○:大気圧解放後、10分以上放置しても液晶は漏出しないが、シール剤への液晶の入り込みが観察された
△:大気圧解放後の放置時間が5分以上、10分未満で液晶が漏出した
×:大気圧解放後の放置時間が5分未満で液晶が漏出した
各実施例および比較例の液晶シール剤に、5μmの球状スペーサーを1質量部さらに添加して、スペーサーが添加された液晶シール剤を調整した。得られた組成物をディスペンサー(日立プラントテクノロジー社製)に充填し、40mm×50mm×厚さ0.7mmの無アルカリガラスの基板の上に35mm×40mm、線幅0.7mmの四角形の枠状のシールパターンを断面積3500μm2で描画した。当該基板のシールパターン内に、貼り合せ後のパネル内容量に相当する液晶材料(MLC-11900-000:メルク社)をディスペンサー(日立プラントテクノロジー社製)にて精密に滴下した。真空貼り合せ装置(信越エンジニアリング社製)にて、10Pa・sの減圧下で前述のガラス基板と対向するガラス基板とを重ね合わせ、荷重をかけ固定した。
実施例6、7、比較例4、5については、固定したサンプルを、紫外線照射装置(ウシオ電機社製)から、100mW/cm2の紫外線を照射し、液晶シール剤を硬化させた。このとき、紫外線の照度エネルギーは2000mJ/cm2とした。光によって液晶シール剤を硬化させた後、オーブンを用いて120℃、60分加熱処理して、液晶表示パネルを作製した。
一方、実施例1~5、8~14、比較例1~3、6~9については、固定したサンプルを、オーブンを用いて120℃、60分加熱処理して液晶表示パネルを作製した。
×:線幅の最大値、最小値の何れか一方、もしくは両方が、線幅の平均値の±20%の範囲に無い場合
〇:線幅の最大値、最小値の両方が、線幅の平均値の±20%以内にあるものの、いずれか一方、もしくは両方が、線幅の平均値の±10%以上である場合
◎:線幅の最大値、最小値の両方が、線幅の平均値の±10%未満の範囲内に有る場合
Claims (11)
- (1a)(メタ)アクリル樹脂、または(1b)分子内にエポキシ基及び(メタ)アクリル基を有する(メタ)アクリル変性エポキシ樹脂と、
(2)平均粒子径4~13μmの有機フィラーAと、
(3)平均粒子径0.05~1μmの有機フィラーBと、
(4)ラジカル重合開始剤と、を含み、
前記成分(2)の含有量(質量)をW1とし、前記成分(3)の含有量(質量)をW2とするとき、
0.25≦W1/(W1+W2)≦0.75である、液晶シール剤。 - 前記W1及び前記W2が、以下の式を満たす、請求項1に記載の液晶シール剤。
0.4≦W1/(W1+W2)≦0.6 - 前記成分(1a)および前記成分(1b)を合わせた樹脂ユニット100質量部に対して、
前記成分(2)及び前記成分(3)の合計量が、20~100質量部である、請求項1に記載の液晶シール剤。 - 前記成分(2)及び前記成分(3)はそれぞれ、シリコーン微粒子、アクリル微粒子、スチレン微粒子、及びポリオレフィン微粒子からなる群より選ばれる一種類以上の微粒子である、請求項1に記載の液晶シール剤。
- 前記成分(1a)及び前記成分(1b)を合わせた樹脂ユニット100質量部に対して、前記成分(4)の含有量が、0.01~3.0質量部である、請求項1に記載の液晶シール剤。
- (5)エポキシ硬化剤をさらに含み、
前記成分(1a)および前記成分(1b)を合わせた樹脂ユニット100質量部に対して、前記成分(5)の含有量が、3~30質量部である、請求項1に記載の液晶シール剤。 - (6)無機フィラーをさらに含み、
前記成分(1a)および前記(1b)を合わせた樹脂ユニット100質量部に対して、前記成分(6)の含有量が、3~30質量部である、請求項1に記載の液晶シール剤。 - (7)遮光剤をさらに含み、
前記(1a)および前記(1b)を合わせた樹脂ユニット100質量部に対して、前記成分(7)の含有量が3~30質量部である、請求項1に記載の液晶シール剤。 - E型粘度計で測定される、25℃、2.5rpmにおける粘度が200~450Pa・sである、請求項1に記載の液晶シール剤。
- 液晶滴下工法による液晶表示パネルの製造に用いられる、請求項1に記載の液晶シール剤。
- 請求項1に記載の液晶シール剤を用いて、一方の基板にシールパターンを形成する工程と、
前記シールパターンが未硬化の状態において、前記一方の基板のシールパターン領域内、または前記一方の基板と対になる他方の基板に液晶を滴下する工程と、
前記一方の基板と、前記他方の基板とを重ね合わせる工程と、
前記シールパターンを硬化させる工程と、を含む液晶表示パネルの製造方法。
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JP2015135444A (ja) * | 2014-01-20 | 2015-07-27 | 日本化薬株式会社 | 液晶シール剤及びそれを用いた液晶表示セル |
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JPWO2017221936A1 (ja) * | 2016-06-21 | 2019-04-11 | 積水化学工業株式会社 | 液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子 |
KR20220066190A (ko) * | 2016-06-21 | 2022-05-23 | 세키스이가가쿠 고교가부시키가이샤 | 액정 표시 소자용 시일제, 상하 도통 재료, 및, 액정 표시 소자 |
KR102531223B1 (ko) | 2016-06-21 | 2023-05-10 | 세키스이가가쿠 고교가부시키가이샤 | 액정 표시 소자용 시일제, 상하 도통 재료, 및, 액정 표시 소자 |
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JP6370382B2 (ja) | 2018-08-08 |
TW201606060A (zh) | 2016-02-16 |
CN106662781B (zh) | 2020-05-15 |
CN106662781A (zh) | 2017-05-10 |
KR20170002632A (ko) | 2017-01-06 |
JPWO2016013214A1 (ja) | 2017-04-27 |
KR101974708B1 (ko) | 2019-05-02 |
TWI673352B (zh) | 2019-10-01 |
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