WO2020022188A1 - Light-blocking sealing agent for liquid crystal dropping methods and method for producing liquid crystal display panel using same - Google Patents
Light-blocking sealing agent for liquid crystal dropping methods and method for producing liquid crystal display panel using same Download PDFInfo
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- WO2020022188A1 WO2020022188A1 PCT/JP2019/028313 JP2019028313W WO2020022188A1 WO 2020022188 A1 WO2020022188 A1 WO 2020022188A1 JP 2019028313 W JP2019028313 W JP 2019028313W WO 2020022188 A1 WO2020022188 A1 WO 2020022188A1
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- liquid crystal
- light
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- agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- 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
Definitions
- the present invention relates to a light-shielding sealant for a liquid crystal dropping method and a method for manufacturing a liquid crystal display panel using the same.
- a liquid crystal display panel has a structure in which a liquid crystal material (hereinafter, also simply referred to as “liquid crystal”) is sandwiched between two transparent substrates provided with electrodes on the surface, and the periphery thereof is sealed with a liquid crystal sealant. It is a panel.
- liquid crystal a liquid crystal material
- liquid crystal sealant Although the amount of the liquid crystal sealant used is small, it is in direct contact with the liquid crystal, which greatly affects the reliability of the liquid crystal display panel. Therefore, in order to achieve high image quality of a liquid crystal display panel, liquid crystal sealants are currently required to have high and various characteristics.
- a liquid crystal dropping method has been widely used as a method of manufacturing a liquid crystal display panel.
- a liquid crystal sealant is applied on a transparent substrate to form a frame for filling the liquid crystal, and (2) fine liquid crystal is dropped into the frame.
- a liquid crystal sealant curable by both light and heat may be used.
- the step (3) after the liquid crystal sealant is temporarily cured by irradiating light such as ultraviolet rays, post-curing by heating can be performed.
- the liquid crystal sealant is in contact with the liquid crystal for a long time in an uncured state. Therefore, the components of the liquid crystal sealant are more easily dissolved in the liquid crystal than in the conventional liquid crystal injection method. Therefore, it has been proposed to increase the photocurability by adding an organic acid to the liquid crystal sealant to suppress the contamination of the liquid crystal (Patent Document 1).
- the seal member black for example, a wide wiring or the like can be covered with the seal member, and a color filter can be arranged on the TFT array side. As a result, the degree of freedom in wiring design is widened, and the brightness of the liquid crystal display panel can be increased.
- the present invention has been made in view of the above problems. That is, a light-shielding sealant for a liquid crystal dropping method, which has good photocurability and can reliably seal between liquid crystal display panel substrates without causing contamination of the liquid crystal, and An object of the present invention is to provide a method for manufacturing a liquid crystal display panel.
- the present invention provides the following light-shielding sealant for a liquid crystal dropping method.
- A an organic acid
- B a photocurable resin having at least one ethylenically unsaturated double bond in one molecule (provided that the (A) organic acid is excluded)
- C A titanocene-based photopolymerization initiator
- D a light-shielding agent having a pH of less than 7.0 or more than 8.0
- E a thermosetting compound having at least one epoxy group in one molecule (provided that ( B) excluding a photocurable resin) and
- F a thermosetting agent, wherein the (A) organic acid has an oxygen atom equivalent represented by the following formula (1) of 23 g / eq or more and 75 g / eq.
- Oxygen atom equivalent (g / eq) (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
- R represents an aromatic or aliphatic hydrocarbon or a derivative thereof
- -P ( O) (OH ) 2 group
- -SO 3 H group at least one functional group selected from the group consisting of -CONH 2 groups
- the light-blocking sealant for a liquid crystal dropping method according to any one of [1] to [3].
- the light-shielding sealant for a liquid crystal dropping method according to any one of [1] to [4], wherein the photocurable resin (B) further has an epoxy group in a molecule.
- the heat curing agent (F) is selected from the group consisting of a dihydrazide heat latent curing agent, an imidazole heat latent curing agent, an amine adduct heat latent curing agent, and a polyamine heat latent curing agent.
- the present invention also provides the following method for manufacturing a liquid crystal display panel.
- the sealant for the liquid crystal dropping method of the present invention has good photocurability despite containing a light-shielding agent. Further, the liquid crystal dropping method sealing agent is unlikely to contaminate the liquid crystal even when it comes into contact with the liquid crystal. Therefore, according to the liquid crystal dropping method sealing agent, a liquid crystal display panel having excellent display reliability can be obtained.
- Light-shielding sealant for liquid crystal dropping method comprises (A) an organic acid, (B) a photocurable resin, and (C) titanocene.
- a system photopolymerization initiator comprises (D) a light-shielding agent, (E) a thermosetting compound, and (F) a thermosetting agent.
- the sealant may contain other components as necessary.
- the light-shielding agent contained in the sealant of the present invention has a pH of less than 7 (more specifically, less than 7.0) or a pH of more than 8.0, and the dispersibility of the light-shielding agent is much better. It is. Although the reason is not clear, if (D) the pH of the light-shielding agent is less than 7 (more specifically, less than 7.0) or if the pH is more than 8.0, (D) other light- It is considered that components (for example, (A) an organic acid, (B) a photocurable resin, and (E) a thermosetting compound) interact with each other.
- components for example, (A) an organic acid, (B) a photocurable resin, and (E) a thermosetting compound
- (D) the dispersibility of the light-shielding agent is improved. If the dispersibility of (D) the light-shielding agent is low, poor curing is likely to occur in a region where the concentration of the (D) light-shielding agent is high, resulting in uneven curability. On the other hand, when the (D) light-shielding agent is uniformly dispersed in the sealant as in the present invention, the curability of the entire sealant becomes uniform.
- the sealant of the present invention contains (A) an organic acid, and the (A) organic acid promotes the photocuring reaction of (B) the photocurable resin. Further, at this time, since the oxygen atom equivalent of (A) the organic acid is within a predetermined range, even if the liquid crystal contacts the (A) organic acid, it hardly affects the liquid crystal.
- the sealant of the present invention contains (C) a titanocene-based photopolymerization initiator having an ability to absorb visible light.
- Light having a relatively long wavelength for example, visible light
- the sealant contains (C) a titanocene-based photopolymerization initiator having an ability to absorb visible light.
- Light having a relatively long wavelength for example, visible light
- the sealant can be activated by such long-wavelength light. Therefore, by using a titanocene-based photopolymerization initiator that can be activated by such long-wavelength light, the deep curability of the sealant can be enhanced.
- the sealant of the present invention has good photocurability even though it contains (D) a light-shielding agent so that its blackness is, for example, 2 to 5. Further, according to the sealing agent, it is possible to reliably seal the space between the substrates of the liquid crystal display panel without causing the liquid crystal to be contaminated by the uncured component.
- the sealing agent contains (A) the organic acid, the photocurability of the sealing agent is enhanced.
- the organic acid (A) may be a Bronsted acid, and the organic acid (A) includes a compound having an acid anhydride structure.
- the organic acid has an oxygen atom equivalent represented by the following formula (1) of 23 g / eq to 75 g / eq, preferably 25 to 60 g / eq, more preferably 27 to 55 g. / Eq.
- Oxygen atom equivalent (g / eq) (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
- the liquid crystal and the organic acid (A) are hardly compatible with each other even when the organic acid (sealant) comes into contact with the liquid crystal during the production of the liquid crystal display panel.
- the liquid crystal is hardly contaminated.
- the oxygen atom equivalent is 75 g / eq or less, even if a small amount of the (A) organic acid is eluted into the liquid crystal, the influence is hardly exerted.
- the organic acid may contain only one kind of these groups, or may contain two or more kinds of these groups.
- organic acids include acetic acid, butyric acid, oxalic acid, citric acid, lauric acid, stearic acid, malonic acid, adipic acid, tartaric acid, benzoic acid, salicylic acid, phthalic acid, monoethyl phosphate, monophenyl phosphate, Diethyl phosphate, mono-2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, benzenesulfonic acid, toluenesulfonic acid, sulfobenzoic acid, formic acid, propionic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargon Acid, capric acid, myristic acid, palmitic acid, margaric acid, succinic acid, glutaric acid, dodecane diacid, sepasic acid, isophthalic acid, terephthalic acid, benzenetricar
- Examples of the organic acid (A) having no ethylenically unsaturated double bond in one molecule include a compound represented by the following formula.
- the organic acid (A) may contain an ethylenically unsaturated double bond in the molecule.
- the (A) organic acid is polymerized with the (B) photocurable resin, and the cured product of the sealant is converted into the (A) organic acid. Is difficult to exude.
- the number of unsaturated double bonds contained in one molecule of the organic acid may be two or more.
- Examples of the (A) organic acid having an unsaturated double bond in one molecule include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (Meth) acryloyloxyethyl phthalic acid, bisphenol A type epoxy (meth) acrylate acid anhydride modified compound, bisphenol A type epoxy (meth) acrylate phosphoric acid modified compound, bisphenol F type epoxy (meth) acrylate acid anhydride modified Compounds, phosphoric acid-modified compounds of bisphenol F type epoxy acrylate, phosphoric acid (meth) acrylates, and high molecular weights thereof are included.
- (meth) acryl means either or both of acryl and methacryl.
- the preferred organic acids (A) include oxalic acid, tartaric acid, trimellitic acid, trimellitic anhydride, isophthalic acid, phenylphosphonic acid, 4'-hydroxy-4-biphenylcarboxylic acid, terephthalic acid, and succinic acid , And glutaric acid.
- the preferred molecular weight of the organic acid (A) is from 60 to 5,000, more preferably from 60 to 3,000, even more preferably from 100 to 1500.
- the (A) organic acid easily flows inside the sealant, and photocuring of the sealant is easily promoted.
- the content of the organic acid (A) is 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the sealant.
- the photocurable resin is not particularly limited as long as it has at least one ethylenically unsaturated double bond in one molecule. However, in this specification, (B) the photocurable resin does not include the compound corresponding to the (A) organic acid.
- Examples of the photocurable resin include (B1) a (meth) acrylic resin and (B2) a (meth) acryl-modified epoxy having at least one epoxy group and one (meth) acryl group in one molecule. Resin included.
- the sealant of the present invention may include both (B1) (meth) acrylic resin and (B2) (meth) acryl-modified epoxy resin.
- the (meth) acrylic resin is a compound containing one or more (meth) acrylic groups in one molecule, and is a compound containing no epoxy group.
- Examples of the (meth) acrylic resin 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 moles or more of ethylene oxide or propylene oxide to 1 mole of pentyl glycol; diacrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A; / Or dimethacrylate; diol of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane.
- triacrylate and / or di or trimethacrylate diacrylate and / or dimethacrylate of a diol obtained by adding at least 4 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A; tris (2-hydroxyethyl) isocyanurate triacrylate; Trimethylolpropane triacrylate and / or trimethacrylate, or an oligomer thereof; pentaerythritol triacrylate and / or trimethacrylate, or an oligomer thereof; polyacrylate and / or polymethacrylate of dipentaerythritol; tris (acryloxy) Ethyl) isocyanurate; caprolactone-modified tris (acryloxyethyl) isocyanate Nurate; caprolactone-modified tris (methacryloxyethyl) isocyanurate; alkyl-modified dipentaerythritol polyacrylate and / or polymethacrylate; cap
- the weight average molecular weight of the (meth) acrylic resin can be, for example, about 310 to 1,000.
- the weight average molecular weight Mw of the (meth) acrylic resin can be measured by gel permeation chromatography (GPC) using polystyrene as a standard.
- the amount of the (B1) (meth) acrylic resin in the sealant is 5 to 80 parts by mass with respect to 100 parts by mass of the sealant, depending on the curability required for the sealant and its blackness. And more preferably 10 to 80 parts by mass.
- the (B2) (meth) acryl-modified epoxy resin is a compound containing at least one each of a (meth) acryl group and an epoxy group.
- the epoxy resin and the (meth) acrylic acid are tertiary, for example. It is a compound obtained by reacting in the presence of a basic catalyst such as an amine.
- the (meth) acryl-modified epoxy resin has an epoxy group and a (meth) acryl group in the molecule, it can have both photocurability and thermosetting properties. Further, the (meth) acryl-modified epoxy resin has low solubility in liquid crystal, and hardly affects the liquid crystal.
- the epoxy resin used as a raw material of the (meth) acryl-modified epoxy resin may be a bifunctional or higher epoxy resin having two or more epoxy groups in a molecule.
- Examples thereof include bisphenol A type and bisphenol F.
- a (meth) acryl-modified epoxy resin obtained by modifying a trifunctional or tetrafunctional polyfunctional epoxy resin with a (meth) acrylic resin has a high crosslinking density and a low adhesion strength to a substrate. Therefore, the epoxy resin used as the raw material of the (B2) (meth) acryl-modified epoxy resin is preferably a bifunctional epoxy resin.
- the bifunctional epoxy resin is preferably a biphenyl type epoxy resin, a naphthalene type epoxy resin, and a bisphenol type epoxy resin.
- bisphenol type epoxy resins such as bisphenol A type and bisphenol F type are preferably used as a sealing agent. It is preferable from the viewpoint of the applicability and the like.
- Epoxy resin as a raw material may be only one kind, or two or more kinds may be combined. Further, it is preferable that the epoxy resin as a raw material is highly purified by a molecular distillation method, a washing method, or the like.
- the (meth) acryl-modified epoxy resin is preferably one in which 10 to 99.5% of the epoxy groups of the epoxy resin as a raw material are modified with (meth) acryl groups, and 30 to 95% % Is more preferably modified with an acrylic group.
- the epoxy group is modified in the above range with a (meth) acrylic group, the photocurability and the thermosetting property of the sealant are improved, and the moisture resistance of the cured product of the sealant is likely to be lowered.
- the weight average molecular weight of the (meth) acryl-modified epoxy resin can be, for example, about 310 to 1,000.
- the weight average molecular weight Mw of the (meth) acryl-modified epoxy resin can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard.
- the amount of the (B2) (meth) acryl-modified epoxy resin in the sealing agent depends on the degree of curability required, but is preferably 5 to 80 parts by mass, and preferably 10 to 80 parts by mass, per 100 parts by mass of the sealing agent. More preferably, it is 80 parts by mass.
- the photocurable resin preferably has a hydrogen-bonding functional group such as a hydroxyl group, a urethane bond, an amide group, and a carboxyl group in the molecule.
- groups may be, for example, hydroxyl groups generated by reacting an epoxy group of an epoxy resin with (meth) acrylic acid, and a compound (B) as a raw material of a photocurable resin (for example, (meth) acrylic acid Or an epoxy resin), or a urethane bond, a carboxyl group, an amide group, or the like contained in a compound as a raw material.
- the equivalent of the hydrogen bonding functional group contained in the photocurable resin is preferably from 1.0 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 3 mol / g, and preferably from 3.5 ⁇ 10 ⁇ 3 to 4. More preferably, it is 5 ⁇ 10 ⁇ 3 mol / g.
- the hydrogen-bonding functional group equivalent is 1.0 ⁇ 10 ⁇ 4 mol / g or more, the dissolution of the photocurable resin (B) in the liquid crystal is easily suppressed.
- the hydrogen bonding functional group equivalent is 5 ⁇ 10 ⁇ 3 mol / g or less
- the cured product of (B) the photocurable resin tends to have sufficient moisture resistance, and the cured product of the sealant has moisture resistance. Is not easily reduced.
- the hydrogen-bonding functional group equivalent (mol / g) of the photocurable resin is represented by "(B) Number of hydrogen-bonding functional groups contained in one molecule of photocurable resin” / "(B) Photocurable Weight average molecular weight (Mw) of the resin ".
- Mw Photocurable Weight average molecular weight
- the hydrogen-bonding functional group equivalent is such that the monomer for obtaining the (B1) (meth) acrylic resin is It can be controlled by adjusting the amount of the hydrogen-bonding functional group contained.
- the (B) photo-curable resin is the above-mentioned (B2) (meth) acryl-modified epoxy resin
- its hydrogen-bonding functional group equivalent is determined, for example, by reacting (meth) acrylic acid with the epoxy resin as a raw material. Can be controlled by adjusting the number of moles, or by adjusting the amount of hydrogen-bonding functional groups contained in the raw material (meth) acrylic acid or epoxy resin.
- the total amount of (B) the photocurable resin (for example, the total amount of (B1) (meth) acrylic resin and (B2) (meth) acryl-modified epoxy resin) is 5 to 80 parts by mass with respect to 100 parts by mass of the sealant. And more preferably 10 to 80 parts by mass.
- the (C) titanocene-based photopolymerization initiator contained in the sealant of the present invention is a compound for curing the (B) photocurable resin described above.
- the use of the (C) titanocene-based photopolymerization initiator can enhance the deep curability of the sealant. Becomes
- titanocene-based photopolymerization initiators include bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl)- Phenyl) titanium, bis (cyclopentadienyl) -dichlorotitanium, bis (cyclopentadienyl) -diphenyltitanium, bis (cyclopentadienyl) -bis (2,3,4,5,6 pentafluorophenyl) titanium , Bis (cyclopentadienyl) -bis (2,6 difluorophenyl) titanium, bis (methylcyclopentadienyl) -bis (2,3,4,5,6 pentafluorophenyl) titanium, bis (methylcyclopenta Dienyl) -bis (2,6-difluorophenyl) titanium, bis (cyclopentadienyl) -bis [2,6-
- ⁇ ⁇ ⁇ it is preferable to be able to absorb light having a wavelength of 300 to 550 nm, and more preferably to be able to absorb light having a wavelength of 350 to 500 nm.
- the content of the titanocene photopolymerization initiator (C) is 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the sealant.
- the sealing agent contains (C) the titanocene-based photopolymerization initiator in the above range, the photocurability of the sealing agent is likely to increase.
- the light-shielding agent contained in the sealant of the present invention has a pH of less than 7 (specifically, less than 7.0) or a pH of more than 8.0 and a blackness of the sealant of, for example, 2 to 5 There is no particular limitation as long as it is adjustable.
- the pH of (D) the light-shielding agent is less than 7 (specifically, less than 7.0) or the pH is more than 8.0, the dispersibility of (D) the light-shielding agent in the sealant is excellent as described above. And the curability of the sealant is improved.
- the pH of the light-shielding agent was determined by diluting and stirring the (D) light-shielding agent 20-fold with pure water, and then measuring the pH of the pure water containing the (D) light-shielding agent with a compact pH meter (B-71X manufactured by HORIBA). It can be obtained by measuring.
- a compact pH meter B-71X manufactured by HORIBA.
- the pH of the light-shielding agent is less than 7.0, it is preferably from 1 to 6, more preferably from 1 to 4.
- the pH of the light-shielding agent (D) exceeds 8.0, the pH is preferably 10.0 or less.
- Examples of the (D) light-blocking agent satisfying the above-mentioned pH include carbon black, titanium black, vanadium, and inorganic compounds such as iron and copper. Among these, it is preferable to include carbon, and examples thereof include acidic carbon black.
- the acidic carbon black may be a channel black or an oxidized carbon black.
- Examples of the method of oxidizing carbon black include air oxidation, nitric acid, mixed gas of nitrogen oxide and air, and oxidation with various oxidizing agents such as ozone.
- the sealing agent may contain only one type of (D) light-shielding agent, or two or more types. Examples of preferable (D) light-shielding agents also include titanium black.
- the shape of the light-shielding agent is not particularly limited, and may be a fixed shape such as a sphere, a plate, or a needle, or an irregular shape.
- the average primary particle diameter of the light-shielding agent (D) is preferably 0.005 to 0.1 ⁇ m, more preferably 0.01 to 0.05 ⁇ m, and more preferably 0.015 to 0.03 ⁇ m. Is more preferable. Average particle diameter It can be measured by a laser diffraction method described in JIS Z8825. The specific surface area can be measured by the BET method described in JIS Z8830.
- the amount of the (D) light-shielding agent with respect to 100 parts by mass of the sealing agent is not particularly limited as long as the blackness of the sealing agent can be adjusted to, for example, 2 to 5.
- the amount can be 5 to 46 parts by mass, preferably 7 to 40 parts by mass, and more preferably 10 to 30 parts by mass with respect to the total amount of the sealant.
- the blackness of the sealing agent tends to fall within a desired range.
- the amount of the (D) light-shielding agent is excessively large, the (D) light-shielding agent is likely to aggregate, and the photocurability of the sealant is likely to be reduced.
- the sealant of the present invention contains (E) a thermosetting compound having at least one epoxy group in one molecule.
- the sealant contains (E) a thermosetting compound, the cured product of the sealant has improved moisture resistance.
- a resin corresponding to the above-mentioned (B) photocurable resin is not included in (E) the thermosetting compound.
- the number of epoxy groups contained in the thermosetting compound is preferably two or more, and particularly preferably two.
- thermosetting compound examples include bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol S type, 2,2′-diallylbisphenol A type, bisphenol AD type, and hydrogenated bisphenol type; Diphenyl ether type epoxy resin; phenol novolak type, cresol novolak type, biphenyl novolak type, bisphenol novolak type, naphthol novolak type, trisphenol novolak type, dicyclopentadiene novolak type, etc .; nophenyl type epoxy resin; biphenyl type epoxy resin; naphthyl type epoxy resin Resins; triphenol alkane type epoxy resins such as triphenol methane type, triphenol ethane type, and triphenol propane type; alicyclic epoxy resins.
- bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol S type, 2,2′-diallylbisphenol A type, bisphenol AD type, and hydrogenated bisphenol type
- Diphenyl ether type epoxy resin phenol
- bisphenol type epoxy resins such as bisphenol A type and bisphenol F type are preferable.
- These bisphenol-type epoxy resins have advantages such as lower crystallinity and superior coating stability than diphenyl ether-type epoxy resins and the like.
- the compound has low solubility and diffusibility in liquid crystal, and not only improves the display characteristics of the obtained liquid crystal display panel, but also increases the moisture resistance of the cured product of the sealant.
- the thermosetting compound preferably has a weight average molecular weight (Mw) of 300 to 3,000, more preferably 300 to 2,000.
- Mw weight average molecular weight
- the weight average molecular weight of the thermosetting compound can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard.
- the thermosetting compound may be liquid or solid.
- the softening point is preferably from 40 ° C to 150 ° C.
- the sealant may contain only one kind of the thermosetting compound (E), or may contain two or more kinds having different kinds and molecular weights.
- the amount of the thermosetting compound (E) is 5 to 70 parts by mass, preferably 5 to 50 parts by mass, based on 100 parts by mass of the sealant.
- thermosetting agent The sealant of the present invention contains (F) a thermosetting agent.
- the (F) thermosetting agent is a compound that contributes to the reaction of the epoxy group contained in the (E) thermosetting compound.
- the photocurable resin (B) has an epoxy group, it also contributes to the reaction of the epoxy group.
- thermosetting agents those that do not generate radicals when reacting with an epoxy group are referred to as (F) thermosetting agents.
- thermosetting agent is not particularly limited, but is preferably a thermal latent curing agent.
- the thermal latent curing agent is a compound which does not cure the (E) thermosetting compound during storage of the sealant (at room temperature), and contributes to the reaction of the epoxy group of the (E) thermosetting compound by heating, (E) A compound that cures a thermosetting compound.
- a known compound can be used as the heat latent curing agent, but a heat latent curing agent having a melting point of 50 ° C. or more and 250 ° C. or less is preferable in order to increase the viscosity stability of the sealant. Further, from the viewpoint of curing the resin even at a low thermosetting temperature (about 80 to 100 ° C.), the melting point is more preferably 50 ° C. or more and 200 ° C. or less.
- Preferred examples of the heat latent curing agent include a dihydrazide heat latent curing agent, an imidazole heat latent curing agent, an amine adduct heat latent curing agent, and a polyamine heat latent curing agent.
- dihydrazide heat latent curing agents examples include adipic dihydrazide (melting point: 181 ° C.), 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (melting point: 120 ° C.), 7,11-octadecadien Includes -1,18-dicarbohydrazide (melting point 160 ° C.), dodecane diacid dihydrazide (melting point 190 ° C.), sebacic acid dihydrazide (melting point 189 ° C.), and the like.
- Preferred examples of the imidazole heat latent curing agent include a compound having a structure represented by the following general formula (X).
- R 1 and R 2 are each independently a hydrogen atom, a lower alkyl group, a lower hydroxyalkyl group, a phenyl group or a benzyl group.
- R 3 and R 4 are each independently a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group. At least one of R 1 to R 4 is a lower hydroxyalkyl group. Since the imidazole-based latent heat curing agent having a lower hydroxyalkyl group contains a hydroxyl group, it is difficult to dissolve in a liquid crystal.
- the lower alkyl group which may be R 1 to R 4 in the above formula (X) is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group, and is preferably a methyl group or an ethyl group.
- the lower hydroxyalkyl group is a hydroxyalkyl group having 1 to 4 carbon atoms such as a hydroxymethyl group and a hydroxyethyl group, and is preferably a hydroxymethyl group.
- the lower hydroxyalkyl group may include a plurality of hydroxyl groups.
- the number of hydroxyl groups contained in the imidazole-based curing catalyst is not particularly limited, but since the water resistance may decrease when the number of hydroxyl groups is 2 or more, the number of hydroxyl groups is 1 in terms of not reducing water resistance and the like. Preferably, there is.
- the melting point of the imidazole heat latent curing agent represented by the general formula (X) depends on the heat curing temperature of the sealant, but when the sealant is thermoset at a relatively low temperature (for example, about 80 to 100 ° C.). Is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 60 to 120 ° C., and particularly preferably 80 to 100 ° C. If the melting point of the imidazole heat latent curing agent is too low, the imidazole heat latent curing agent will melt at room temperature. Then, (E) the curing reaction of the thermosetting compound proceeds, and the storage stability of the sealant at room temperature deteriorates.
- a relatively low temperature for example, about 80 to 100 ° C.
- the melting point of the imidazole heat latent curing agent can be lowered by, for example, having a structure not containing an aromatic ring.
- R 2 is preferably a group other than a phenyl group or a benzyl group, that is, a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group, and a lower hydroxyalkyl group. Is more preferable.
- Examples of the imidazole heat latent curing agent represented by the general formula (X) include 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-hydroxy Methyl imidazole, 1-benzyl-5-hydroxymethyl imidazole, 1,2-dihydroxyethyl imidazole and the like are included.
- examples of the imidazole-based heat latent curing agent having a melting point of 150 ° C. or lower include 2-hydroxymethylimidazole.
- the amine adduct thermal latent curing agent is an additional compound obtained by reacting an amine compound having catalytic activity with an arbitrary compound.
- the amine is dissociated by heat and activated.
- Examples of the amine-based compound include compounds having 1, 2, and tertiary amino groups, such as Amicure PN-40 (melting point 110 ° C.), Amicure PN-23 (melting point 100 ° C.), and Amicure PN-31 ( Melting point 115 ° C.), AMICURE PN-24 (melting point 115 ° C.), AMICURE MY-24 (melting point 120 ° C.), AMICURE MY-H (melting point 130 ° C.) (all manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.
- Amicure PN-40 melting point 110 ° C.
- Amicure PN-23 melting point 100 ° C.
- Amicure PN-31 Melting point 115 ° C.
- AMICURE PN-24 melting point 115 ° C.
- AMICURE MY-24 melting point 120 ° C.
- AMICURE MY-H melting point 130 ° C.
- the polyamine-based heat latent curing agent is a heat latent curing agent having a polymer structure obtained by reacting an amine with an epoxy, and specific examples thereof include Adeka Hardener EH4339S (softening point of 120 to 130) manufactured by ADEKA Corporation. ° C) and Adeka Hardener EH4357S (softening point 73-83 ° C) manufactured by ADEKA Corporation.
- thermosetting agent (F) is preferably 5 to 100 parts by mass, more preferably 10 to 100 parts by mass, based on 100 parts by mass of the total of (B) the photocurable resin and (E) the thermosetting compound. It is 50 parts by mass or less. (F) When a thermosetting agent is contained, the thermosetting reaction of the sealing agent easily proceeds sufficiently.
- the sealant of the present invention may contain components other than those described above. Examples of other components include inorganic fillers and organic fillers, various additives, and the like.
- the viscosity of the sealant can be adjusted to a desired range, and the strength and linear expansion of a cured product of the sealant can be controlled.
- the inorganic filler include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, and talc.
- the sealant may include only one of these, or may include two or more thereof.
- the shape of the inorganic filler is not particularly limited, and may be any of a fixed shape such as a sphere, a plate, and a needle, or an irregular shape.
- the inorganic filler preferably has an average primary particle diameter of 1.5 ⁇ m or less, and preferably has a specific surface area of 1 m 2 / g to 500 m 2 / g.
- the average primary particle diameter of the inorganic filler can be measured by a laser diffraction method described in JIS Z8825.
- the specific surface area can be measured by the BET method described in JIS Z8830.
- the amount of the inorganic filler is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the sealant.
- the sealant contains an organic filler
- the impact resistance and the like of the sealant are improved.
- the type of the organic filler is not particularly limited, but the melting point of the sealant is preferably higher than the thermosetting temperature.
- the softening point of the organic filler is preferably 30 to 120 ° C.
- organic filler examples 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 sealant may contain only one type of organic filler, or may contain two or more types of organic filler.
- the shape of the organic filler is not particularly limited, and may be, for example, spherical.
- the average particle size of the organic filler is preferably 0.05 to 5 ⁇ m, more preferably 0.07 to 3 ⁇ m, since the gap of the liquid crystal cell is usually 5 ⁇ m or less.
- the average particle size of the organic filler can be measured, for example, by a laser diffraction method described in JIS Z8825.
- the amount of the organic filler is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the sealant.
- additives examples include a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a plasticizer, a defoaming agent, and the like. Further, a spacer or the like may be blended for adjusting the gap of the liquid crystal display panel. These contents are not particularly limited as long as the objects and effects of the present invention are not impaired.
- the above-mentioned sealant preferably has a blackness of 2 to 5, more preferably 3 to 4.
- the blackness of the sealant can be measured as follows.
- a sealing agent is collected with a spatula, and dropped on a 25 mm ⁇ 45 mm ⁇ 5 mm thick non-alkali glass to form a circle having a diameter of 5 mm. Then, a pair of non-alkali glass is attached so as to overlap with each other and fixed with a jig.
- the test piece fixed with the jig is irradiated with an ultraviolet ray of 500 mW / cm 2 from an ultraviolet ray irradiation device (manufactured by Ushio Inc.) to cure the sealant. At this time, the illuminance energy of the ultraviolet light is 3.0 J / cm 2 .
- the viscosity of the sealant at 25 ° C. and 2.5 rpm using an E-type viscometer is preferably 30 to 350 Pa ⁇ s.
- a liquid crystal sealant having a viscosity in the above range has excellent coating stability.
- the method for producing the above-mentioned sealant is not particularly limited, and all the components may be mixed, or the components may be mixed twice or more.
- the mixing method is not particularly limited, but is preferably a method capable of sufficiently dispersing the (D) light-shielding agent, such as a three-roll mill.
- the liquid crystal display panel is usually a display substrate, a counter substrate to be paired with the display substrate, a frame-shaped sealing member interposed between the display substrate and the counter substrate, a display substrate and the counter substrate. And a liquid crystal layer filled in a space surrounded by the seal member.
- a cured product of the above-described sealant can be used as a seal member.
- Both the display substrate and the counter substrate are 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, color filter, black matrix, and the like are 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 or inorganic alignment agent.
- a black matrix and a color filter may be arranged on a display substrate side, a black matrix may be arranged on a display substrate side, and a color filter may be arranged on a counter substrate side.
- a black matrix and a color filter may be arranged on the substrate side.
- Such a liquid crystal display panel can be manufactured by the following method. Specifically, 1) a first step of applying the above-mentioned sealant to one substrate to form a liquid crystal seal pattern, and 2) the liquid crystal in a state where the liquid crystal seal pattern made of the sealant is uncured. A second step of dropping liquid crystal on a region surrounded by a seal pattern or a region of the other substrate facing the region surrounded by the liquid crystal seal pattern; 3) forming one substrate and the other substrate , A third step of superimposing via a liquid crystal seal pattern, and 4) a fourth step of curing the sealant.
- the above-mentioned sealant is applied in a desired pattern.
- the method for applying the sealant is not particularly limited as long as the sealant can be applied to a desired region, and may be, for example, an application using a dispenser.
- the liquid crystal seal pattern to be manufactured is appropriately selected according to the type of the liquid crystal display panel and the like, and can be usually formed in a rectangular frame shape or the like.
- the line width of the sealant in the liquid crystal seal pattern is preferably 300 to 2000 ⁇ m, more preferably 500 to 1500 ⁇ m.
- Sectional area of the sealing agent is preferably 1000 ⁇ 10000 2, more preferably 1500 ⁇ 5000 ⁇ m 2.
- liquid crystal is applied in a state where the liquid crystal seal pattern produced in the first step is in an uncured state.
- the method of dropping the liquid crystal is not particularly limited, and may be a known method.
- the “state in which the liquid crystal seal pattern is not cured” means a state in which the curing reaction of the sealant has not progressed to the gel point. Therefore, in the second step, the liquid crystal seal pattern may be semi-cured by irradiating or heating the liquid crystal in order to suppress the dissolution of the sealant into the liquid crystal.
- one substrate and the other substrate are overlapped via a liquid crystal seal pattern.
- the superposition can be performed by a known method, and is usually performed under a high vacuum.
- the sealant is cured. It is preferable that the sealing agent is cured by heating (main curing) after being subjected to light curing (temporary curing). By instantly curing the sealant by temporary curing by light irradiation, dissolution in liquid crystal can be suppressed.
- the sealant of the present invention contains (C) a titanocene-based photopolymerization initiator. Therefore, the irradiation light preferably includes not only ultraviolet light but also light in the visible light region. In this specification, the visible light region refers to a wavelength range from 360 nm to 800 nm.
- the light source is not particularly limited, but is preferably an LED, a metal halide lamp, a high-pressure mercury lamp, or a low-pressure mercury lamp, and more preferably an LED or a metal halide lamp. From the viewpoint of sufficiently activating the (C) titanocene-based photopolymerization initiator, the wavelength preferably ranges from 360 to 550 nm, and more preferably ranges from 360 to 450 nm.
- the heating temperature at the time of heating after light irradiation depends on the composition of the sealing agent, but is preferably as low as possible, for example, about 120 ° C., from the viewpoint of reducing deterioration of the liquid crystal.
- the temperature is more preferably 80 to 120 ° C.
- the heat curing time is about 1 to 2 hours.
- the obtained compound was washed 20 times with ultrapure water, and a methacrylic acid-modified bisphenol F-type epoxy resin (95% partially methacrylated) (weight average molecular weight (Mw) 485, hydrogen bonding functional group equivalent 4.0 ⁇ ). 10 ⁇ 3 mol / g).
- Example 1 As a photocurable resin, 330 parts by mass of a methacrylic acid-modified bisphenol F type epoxy resin obtained in a synthesis example and polyethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate 14EG-A, weight average molecular weight 722, hydrogen bonding) 172 parts by mass of a functional group equivalent (0.9 ⁇ 10 ⁇ 3 mol / g), 6 parts by mass of (A) trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd., oxygen atom equivalent 35 g / eq) as an organic acid, and (C) ) 12 parts by mass of a titanocene-based photopolymerization initiator (manufactured by Insight High Technology: IHT-PI 784) and (E) an epoxy resin as a thermosetting compound (manufactured by Mitsubishi Chemical Corporation: jER1004, softening point 97 ° C, weight average
- Example 2 A sealant was obtained in the same manner as in Example 1 except that the content was changed to the content shown in Table 1.
- Example 3 A sealant was used in the same manner as in Example 1 except that carbon (Mitsubishi Chemical Corporation: # 2600, pH 6.5, particle size: 13 nm) was used instead of carbon (MA-100R) as a light-shielding agent. I got
- Example 4 Sealing agent in the same manner as in Example 1, except that titanium black (13M, pH 8.8, particle diameter 97 nm, manufactured by Mitsubishi Materials Corporation) was used instead of carbon (MA-100R) as a light-shielding agent. I got
- Example 5 A sealant was obtained in the same manner as in Example 1, except that phenylphosphonic acid (oxygen atom equivalent: 53 g / eq) was used as the organic acid instead of trimellitic acid.
- Example 1 A sealant was obtained in the same manner as in Example 1, except that trimellitic acid was not added, and t-butyl peroxypivalate (manufactured by Mitsubishi Chemical: Luperox 11) was added as a thermal radical generator.
- the test piece cured by light was heated in an oven at 120 ° C. for 60 minutes to obtain a sample for measuring blackness.
- the seal pattern was a circle having a diameter of 5 mm.
- a pair of non-alkali glass was stuck together so as to overlap, and fixed with a jig.
- the test piece fixed with the jig was irradiated with ultraviolet light (wavelength 365 nm) of 500 mW / cm 2 from an ultraviolet irradiation device (manufactured by Ushio Inc.) to cure the sealant.
- the illuminance energy of the ultraviolet light was 3.0 J / cm 2 .
- the test piece cured by light was heated in an oven at 120 ° C. for 60 minutes to obtain a sample for dispersibility evaluation. This sample was observed with a microscope, and the number of foreign substances (aggregates of light-shielding agents) present in a visual field of 2 mm ⁇ 2 mm was counted.
- ⁇ No foreign matter
- ⁇ Less than 10 foreign matters
- ⁇ 10 or more foreign matters
- a liquid crystal material manufactured by MLC-7021-00 Merck Co., Ltd.
- a dispenser After bonding the glass substrates to be paired under reduced pressure, they were opened to the atmosphere and bonded. Thereafter, light of 1000 mJ / cm 2 (light calibrated by a sensor having a wavelength of 365 nm) is irradiated in a state where the black matrix is covered with a substrate formed with a line / space of 300 ⁇ m / 100 ⁇ m so as to cover the lower half of the main seal. And further heated at 120 ° C. for 1 hour.
- the liquid crystal display panel after the hardening treatment of the light shielding sealant was evaluated as follows. :: No liquid crystal leakage occurred ⁇ : No liquid crystal leakage occurred, but liquid crystal was inserted into sealant ⁇ : Liquid crystal leakage occurred
- the sealant was printed on a 25 mm ⁇ 45 mm ⁇ 5 mm thick non-alkali glass using a screen plate.
- the seal pattern was a circle having a diameter of 1 mm. Then, they were mounted on a pair of non-alkali glass in a seal pattern and fixed with a jig.
- the test piece fixed by the jig was irradiated with an ultraviolet ray (wavelength: 365 nm) of 500 mW / cm 2 by an ultraviolet ray irradiation device (manufactured by Ushio Inc.) to cure the light-shielding sealant.
- the illuminance energy of the ultraviolet rays was 3.0 J / cm 2 .
- the test piece obtained by curing the light-shielding sealant with light was heated at 120 ° C. for 60 minutes using an oven to obtain a sample for measuring the adhesive strength.
- the tensile speed was set to 2 mm / min, and the cured light-shielding sealant was peeled off in a direction parallel to the glass bottom surface to measure the tensile strength in a plane.
- the adhesive strength was evaluated in the following four stages according to the magnitude of the plane tensile strength.
- ⁇ Tensile strength of 15 MPa or more
- ⁇ Tensile strength of 10 MPa or more and less than 15 MPa
- the stability was evaluated as follows. ((Excellent): The ratio of the viscosity after one week to the initial viscosity (increase rate) was 1.2 times or less. ⁇ (somewhat excellent): The ratio of the viscosity after one week to the initial viscosity (increase rate) was 1 X: less than 1.5 times ⁇ (poor): The ratio of the viscosity after one week to the initial viscosity (increase rate) exceeded 1.5 times
- the sealant of the present invention has high photocurability and can reliably seal between substrates of a liquid crystal display panel without causing contamination of liquid crystal. Therefore, a highly reliable display panel can be manufactured, which is suitable for manufacturing various liquid crystal display panels.
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Abstract
Description
[1](A)有機酸と、(B)1分子内にエチレン性不飽和二重結合を少なくとも1つ有する光硬化性樹脂(ただし、前記(A)有機酸を除く)と、(C)チタノセン系光重合開始剤と、(D)pHが7.0未満または8.0を超える遮光剤と、(E)1分子内にエポキシ基を少なくとも1つ有する熱硬化性化合物(ただし、前記(B)光硬化性樹脂を除く)と、(F)熱硬化剤と、を含み、前記(A)有機酸の下記式(1)で表される酸素原子当量が、23g/eq以上75g/eq以下である、液晶滴下工法用遮光シール剤。
酸素原子当量(g/eq)=(有機酸の分子量)/(有機酸1分子中の酸素原子数)・・(1) The present invention provides the following light-shielding sealant for a liquid crystal dropping method.
[1] (A) an organic acid, (B) a photocurable resin having at least one ethylenically unsaturated double bond in one molecule (provided that the (A) organic acid is excluded), and (C) A titanocene-based photopolymerization initiator, (D) a light-shielding agent having a pH of less than 7.0 or more than 8.0, and (E) a thermosetting compound having at least one epoxy group in one molecule (provided that ( B) excluding a photocurable resin) and (F) a thermosetting agent, wherein the (A) organic acid has an oxygen atom equivalent represented by the following formula (1) of 23 g / eq or more and 75 g / eq. The following is a light-shielding sealant for a liquid crystal dropping method.
Oxygen atom equivalent (g / eq) = (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
[3]前記(D)遮光剤が炭素およびチタンのうち、少なくとも一方を含む、[1]または[2]に記載の液晶滴下工法用遮光シール剤。
[4]前記(A)有機酸が1分子内に、-OH基、-NH2基、-NHR基(Rは、芳香族、脂肪族炭化水素又はこれらの誘導体を表す)、-COOH基、-OP(=O)(OH)2基、-P(=O)(OH)2基、-SO3H基、-CONH2基、および-NHOH基からなる群より選ばれる官能基を少なくとも1つ有する、[1]~[3]のいずれかに記載の液晶滴下工法用遮光シール剤。 [2] The light-shielding sealant according to [1], which has a blackness of 2 to 5.
[3] The light-shielding sealant according to [1] or [2], wherein the light-shielding agent (D) contains at least one of carbon and titanium.
[4] The organic acid (A) includes, in one molecule, an —OH group, a —NH 2 group, a —NHR group (R represents an aromatic or aliphatic hydrocarbon or a derivative thereof), a —COOH group, -OP (= O) (OH) 2 group, -P (= O) (OH ) 2 group, -SO 3 H group, at least one functional group selected from the group consisting of -CONH 2 groups, and -NHOH group The light-blocking sealant for a liquid crystal dropping method according to any one of [1] to [3].
[6]前記(F)熱硬化剤が、ジヒドラジド系熱潜在性硬化性、イミダゾール系熱潜在性硬化剤、アミンアダクト系熱潜在性硬化剤、およびポリアミン系熱潜在性硬化剤からなる群より選ばれる1以上である、[1]~[5]のいずれかに記載の液晶滴下工法用遮光シール剤。 [5] The light-shielding sealant for a liquid crystal dropping method according to any one of [1] to [4], wherein the photocurable resin (B) further has an epoxy group in a molecule.
[6] The heat curing agent (F) is selected from the group consisting of a dihydrazide heat latent curing agent, an imidazole heat latent curing agent, an amine adduct heat latent curing agent, and a polyamine heat latent curing agent. The light-shielding sealant for a liquid crystal dropping method according to any one of [1] to [5], which is one or more of the following.
[7]上記[1]~[6]のいずれかに記載の液晶滴下工法用遮光シール剤を用いて、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、前記シールパターンの領域内、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、前記シールパターンを介して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。 The present invention also provides the following method for manufacturing a liquid crystal display panel.
[7] A step of forming a seal pattern on one of the substrates using the light-shielding sealant for a liquid crystal dropping method according to any one of [1] to [6], and In the region of the seal pattern, or a step of dropping liquid crystal on the other substrate paired with the one substrate, and the step of superimposing the one substrate and the other substrate via the seal pattern, And a step of curing the seal pattern.
[9]前記シールパターンに照射する光は、可視光領域の光を含む、[8]に記載の液晶表示パネルの製造方法。
[10]前記シールパターンを硬化させる工程は、光が照射された前記シールパターンを加熱して硬化させる工程をさらに含む、[8]または[9]に記載の液晶表示パネルの製造方法。 [8] The method for manufacturing a liquid crystal display panel according to [7], wherein the step of curing the seal pattern includes a step of irradiating the seal pattern with light to cure the seal pattern.
[9] The method for manufacturing a liquid crystal display panel according to [8], wherein the light applied to the seal pattern includes light in a visible light region.
[10] The method for manufacturing a liquid crystal display panel according to [8] or [9], wherein the step of curing the seal pattern further includes a step of heating and curing the seal pattern irradiated with light.
本発明の液晶滴下工法用遮光シール剤(以下、単に「シール剤」とも称する)は、(A)有機酸と、(B)光硬化性樹脂と、(C)チタノセン系光重合開始剤と、(D)遮光剤と、(E)熱硬化性化合物と、(F)熱硬化剤と、を含む。シール剤は、必要に応じてこれら以外の成分を含んでいてもよい。 1. Light-shielding sealant for liquid crystal dropping method The light-shielding sealant for liquid crystal dropping method (hereinafter also simply referred to as “sealant”) of the present invention comprises (A) an organic acid, (B) a photocurable resin, and (C) titanocene. A system photopolymerization initiator, (D) a light-shielding agent, (E) a thermosetting compound, and (F) a thermosetting agent. The sealant may contain other components as necessary.
前述のように、シール剤に(A)有機酸が含まれると、シール剤の光硬化性が高まる。本明細書において、(A)有機酸は、ブレンステッド酸であればよく、(A)有機酸には、酸無水物構造を有する化合物も含むものとする。 (A) Organic Acid As described above, when the sealing agent contains (A) the organic acid, the photocurability of the sealing agent is enhanced. In this specification, the organic acid (A) may be a Bronsted acid, and the organic acid (A) includes a compound having an acid anhydride structure.
酸素原子当量(g/eq)=(有機酸の分子量)/(有機酸1分子中の酸素原子数)・・(1) Here, (A) the organic acid has an oxygen atom equivalent represented by the following formula (1) of 23 g / eq to 75 g / eq, preferably 25 to 60 g / eq, more preferably 27 to 55 g. / Eq.
Oxygen atom equivalent (g / eq) = (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
(B)光硬化性樹脂は、エチレン性不飽和二重結合を1分子内に少なくとも1つ有する樹脂であれば特に制限されない。ただし、本明細書において、(B)光硬化性樹脂には、前述の(A)有機酸に相当する化合物は含まないものとする。(B)光硬化性樹脂の例には、(B1)(メタ)アクリル樹脂や、(B2)1分子内にエポキシ基と(メタ)アクリル基とをそれぞれ少なくとも1つ有する(メタ)アクリル変性エポキシ樹脂が含まれる。 (B) Photocurable resin (B) The photocurable resin is not particularly limited as long as it has at least one ethylenically unsaturated double bond in one molecule. However, in this specification, (B) the photocurable resin does not include the compound corresponding to the (A) organic acid. (B) Examples of the photocurable resin include (B1) a (meth) acrylic resin and (B2) a (meth) acryl-modified epoxy having at least one epoxy group and one (meth) acryl group in one molecule. Resin included.
本発明のシール剤が含む(C)チタノセン系光重合開始剤は、前述の(B)光硬化性樹脂を硬化させるための化合物である。前述のように、(C)チタノセン系光重合開始剤は、可視光吸収能を有するため、当該(C)チタノセン系光重合開始剤を用いることで、シール剤の深部硬化性を高めることが可能となる。 (C) Titanocene-based photopolymerization initiator The (C) titanocene-based photopolymerization initiator contained in the sealant of the present invention is a compound for curing the (B) photocurable resin described above. As described above, since the (C) titanocene-based photopolymerization initiator has a visible light absorbing ability, the use of the (C) titanocene-based photopolymerization initiator can enhance the deep curability of the sealant. Becomes
本発明のシール剤が含む遮光剤は、pHが7未満(詳しくは7.0未満)、もしくはpHが8.0超であり、かつシール剤の黒色度を例えば2~5に調整可能なものであれば特に制限されない。(D)遮光剤のpHが7未満(詳しくは7.0未満)、もしくはpHが8.0超であると、上述のように(D)遮光剤のシール剤中での分散性が良好になり、シール剤の硬化性が良好になる。 (D) Light-Shielding Agent The light-shielding agent contained in the sealant of the present invention has a pH of less than 7 (specifically, less than 7.0) or a pH of more than 8.0 and a blackness of the sealant of, for example, 2 to 5 There is no particular limitation as long as it is adjustable. When the pH of (D) the light-shielding agent is less than 7 (specifically, less than 7.0) or the pH is more than 8.0, the dispersibility of (D) the light-shielding agent in the sealant is excellent as described above. And the curability of the sealant is improved.
本発明のシール剤は、(E)1分子内にエポキシ基を少なくとも1つ有する熱硬化性化合物を含む。シール剤が(E)熱硬化性化合物を含むと、シール剤の硬化物の耐湿性が高まる。なお、本明細書において、上述の(B)光硬化性樹脂に相当する樹脂は、(E)熱硬化性化合物に含まない。(E)熱硬化性化合物が含むエポキシ基の数は、2以上であることが好ましく、2つであることが特に好ましい。 (E) Thermosetting Compound The sealant of the present invention contains (E) a thermosetting compound having at least one epoxy group in one molecule. When the sealant contains (E) a thermosetting compound, the cured product of the sealant has improved moisture resistance. In this specification, a resin corresponding to the above-mentioned (B) photocurable resin is not included in (E) the thermosetting compound. (E) The number of epoxy groups contained in the thermosetting compound is preferably two or more, and particularly preferably two.
本発明のシール剤は、(F)熱硬化剤を含む。(F)熱硬化剤は、(E)熱硬化性化合物が含むエポキシ基の反応に寄与する化合物である。なお、(B)光硬化性樹脂がエポキシ基を有する場合には、当該エポキシ基の反応にも寄与する。本明細書では、エポキシ基と反応する際に、ラジカルを発生しないものを(F)熱硬化剤とする。 (F) Thermosetting agent The sealant of the present invention contains (F) a thermosetting agent. The (F) thermosetting agent is a compound that contributes to the reaction of the epoxy group contained in the (E) thermosetting compound. When the photocurable resin (B) has an epoxy group, it also contributes to the reaction of the epoxy group. In the present specification, those that do not generate radicals when reacting with an epoxy group are referred to as (F) thermosetting agents.
本発明のシール剤は、上述した以外の成分を含んでいてもよい。その他の成分の例には、無機フィラーや有機フィラー、各種添加剤等が含まれる。 (G) Others The sealant of the present invention may contain components other than those described above. Examples of other components include inorganic fillers and organic fillers, various additives, and the like.
上述のシール剤は、黒色度が好ましくは2~5であり、3~4であることがより好ましい。シール剤の黒色度は、以下のように測定することができる。 -Physical properties of sealant and manufacturing method The above-mentioned sealant preferably has a blackness of 2 to 5, more preferably 3 to 4. The blackness of the sealant can be measured as follows.
液晶表示パネルは通常、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。本発明では、上述のシール剤の硬化物を、シール部材とすることができる。 2. Liquid crystal display panel manufacturing method The liquid crystal display panel is usually a display substrate, a counter substrate to be paired with the display substrate, a frame-shaped sealing member interposed between the display substrate and the counter substrate, a display substrate and the counter substrate. And a liquid crystal layer filled in a space surrounded by the seal member. In the present invention, a cured product of the above-described sealant can be used as a seal member.
・メタアクリル酸変性ビスフェノールF型エポキシ樹脂の合成
160gの液状ビスフェノールF型エポキシ樹脂(エポトートYDF-8170C 東都化成社製 エポキシ当量160g/eq)、重合禁止剤として0.1gのp-メトキシフェノール、触媒として0.2gのトリエタノールアミン、および81.7gのメタクリル酸をフラスコ内に仕込み、乾燥空気を送り込んで90℃で還流攪拌しながら5時間反応させた。得られた化合物を、超純水にて20回洗浄し、メタクリル酸変性ビスフェノールF型エポキシ樹脂(95%部分メタクリル化物)(重量平均分子量(Mw)485、水素結合性官能基当量4.0×10-3mol/g)を得た。 [Synthesis example]
-Synthesis of methacrylic acid-modified bisphenol F type epoxy resin 160 g of liquid bisphenol F type epoxy resin (Epototo YDF-8170C manufactured by Toto Kasei Co., Ltd., epoxy equivalent 160 g / eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, catalyst Was charged into a flask, and dry air was fed thereinto, and the mixture was reacted at 90 ° C. for 5 hours while stirring under reflux. The obtained compound was washed 20 times with ultrapure water, and a methacrylic acid-modified bisphenol F-type epoxy resin (95% partially methacrylated) (weight average molecular weight (Mw) 485, hydrogen bonding functional group equivalent 4.0 ×). 10 −3 mol / g).
(B)光硬化性樹脂として、合成例で得られたメタクリル酸変性ビスフェノールF型エポキシ樹脂330質量部およびポリエチレングリコールジアクリレート(共栄社化学社製:ライトアクリレート14EG-A、重量平均分子量722、水素結合性官能基当量0.9×10-3mol/g)172質量部と、(A)有機酸としてトリメリット酸(東京化成工業社製、酸素原子当量35g/eq)6質量部と、(C)チタノセン系光重合開始剤(Insight High Technology社製:IHT-PI 784)12質量部と、(E)熱硬化性化合物としてエポキシ樹脂(三菱ケミカル社製:jER1004、軟化点97℃、重量平均分子量1650)50質量部と、(F)熱硬化剤としてアジピン酸ジヒドラジド(日本化成社製:ADH、融点177~184℃)90質量部と、シリカ粒子(日本触媒化学社製:S-100)80質量部と、熱可塑性樹脂粒子(微粒子ポリマー、アイカ工業社製:F351)40質量部と、シランカップリング剤(信越化学工業社製:KBM-403)20質量部と、(D)遮光剤としてカーボン(三菱ケミカル社製:MA-100R、pH3.5、粒子径24nm)200質量部とを、三本ロールを用いて均一な液となるように十分に混合して、シール剤を得た。なお、(D)遮光剤のpHは、(D)遮光剤を純水で20倍に希釈・攪拌した後、(D)遮光剤を含む純水のpHを、HORIBA社製コンパクトpHメーター B-71Xで測定することにより求めた。また、(A)有機酸の酸素原子当量は、以下の式(1)から求めた。
酸素原子当量(g/eq)=(有機酸の分子量)/(有機酸1分子中の酸素原子数)・・(1) [Example 1]
(B) As a photocurable resin, 330 parts by mass of a methacrylic acid-modified bisphenol F type epoxy resin obtained in a synthesis example and polyethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate 14EG-A, weight average molecular weight 722, hydrogen bonding) 172 parts by mass of a functional group equivalent (0.9 × 10 −3 mol / g), 6 parts by mass of (A) trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd., oxygen atom equivalent 35 g / eq) as an organic acid, and (C) ) 12 parts by mass of a titanocene-based photopolymerization initiator (manufactured by Insight High Technology: IHT-PI 784) and (E) an epoxy resin as a thermosetting compound (manufactured by Mitsubishi Chemical Corporation: jER1004, softening point 97 ° C, weight average molecular weight) 1650) 50 parts by mass, and (F) adipic dihydrazide (manufactured by Nippon Kasei Co., Ltd.) as a thermosetting agent : ADH, melting point: 177 to 184 ° C) 90 parts by mass, silica particles (S-100 manufactured by Nippon Shokubai Kagaku Co., Ltd .: 80 parts by mass), and thermoplastic resin particles (fine particle polymer, manufactured by Aika Kogyo Co., Ltd .: F351) 40 parts by mass And 20 parts by mass of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403) and (D) 200 parts by mass of carbon (manufactured by Mitsubishi Chemical Corporation: MA-100R, pH 3.5, particle diameter 24 nm) as a light shielding agent Was thoroughly mixed using a three-roll mill so that a uniform liquid was obtained, to obtain a sealant. The pH of the light-shielding agent (D) was determined by diluting (D) the light-shielding agent 20-fold with pure water and stirring, and then measuring the pH of the pure water containing the light-shielding agent (B) using a compact pH meter B- manufactured by HORIBA. It was determined by measuring at 71X. Further, (A) the oxygen atom equivalent of the organic acid was determined from the following equation (1).
Oxygen atom equivalent (g / eq) = (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
表1に記載の含有量に変更した以外は、実施例1と同様にしてシール剤を得た。 [Example 2]
A sealant was obtained in the same manner as in Example 1 except that the content was changed to the content shown in Table 1.
(D)遮光剤として、カーボン(MA-100R)の代わりに、カーボン(三菱ケミカル社製:#2600、pH6.5、粒子径13nm)を用いた以外は、実施例1と同様にしてシール剤を得た。 [Example 3]
(D) A sealant was used in the same manner as in Example 1 except that carbon (Mitsubishi Chemical Corporation: # 2600, pH 6.5, particle size: 13 nm) was used instead of carbon (MA-100R) as a light-shielding agent. I got
(D)遮光剤として、カーボン(MA-100R)の代わりに、チタンブラック(三菱マテリアル社製:13M、pH8.8、粒子径97nm)を用いた以外は、実施例1と同様にしてシール剤を得た。 [Example 4]
(D) Sealing agent in the same manner as in Example 1, except that titanium black (13M, pH 8.8, particle diameter 97 nm, manufactured by Mitsubishi Materials Corporation) was used instead of carbon (MA-100R) as a light-shielding agent. I got
(A)有機酸として、トリメリット酸の代わりに、フェニルホスホン酸(酸素原子当量53g/eq)を用いた以外は、実施例1と同様にしてシール剤を得た。 [Example 5]
(A) A sealant was obtained in the same manner as in Example 1, except that phenylphosphonic acid (oxygen atom equivalent: 53 g / eq) was used as the organic acid instead of trimellitic acid.
トリメリット酸を添加せずに、熱ラジカル発生剤としてt-ブチル パーオキシピバレート(三菱ケミカル製:ルペロックス11)を添加した以外は、実施例1と同様にしてシール剤を得た。 [Comparative Example 1]
A sealant was obtained in the same manner as in Example 1, except that trimellitic acid was not added, and t-butyl peroxypivalate (manufactured by Mitsubishi Chemical: Luperox 11) was added as a thermal radical generator.
トリメリット酸を添加せずに、表1に記載の含有量に変更した以外は、実施例1と同様にしてシール剤を得た。 [Comparative Example 2]
A sealant was obtained in the same manner as in Example 1 except that the content was changed to the content shown in Table 1 without adding trimellitic acid.
チタノセン系光重合開始剤およびトリメリット酸を添加せず、オキシムエステル系光重合開始剤(BASF社製:IRGACURE OXE-1、1.2-オクタンジオン1-[4-(フェニルチオ)-2-(O-ベンゾイルオキシム)])を添加して、表1に記載の含有量に変更した以外は、実施例1と同様にしてシール剤を得た。 [Comparative Example 3]
Without adding a titanocene-based photopolymerization initiator and trimellitic acid, an oxime ester-based photopolymerization initiator (manufactured by BASF: IRGACURE OXE-1, 1.2-octanedione 1- [4- (phenylthio) -2- ( O-benzoyl oxime)]) was added to obtain a sealant in the same manner as in Example 1 except that the content was changed to the content shown in Table 1.
(D)遮光剤として、カーボン(MA-100R)の代わりに、カーボン(旭カーボン社製:SB200、pH7.5、粒子径26nm)を用いた以外は、実施例1と同様にしてシール剤を得た。 [Comparative Example 4]
(D) A sealing agent was used in the same manner as in Example 1 except that carbon (manufactured by Asahi Carbon: SB200, pH 7.5, particle size: 26 nm) was used instead of carbon (MA-100R) as a light-shielding agent. Obtained.
(A)有機酸としてトリメリット酸の代わりに、2-エチルヘキシルホスフェート(酸素原子当量81g/eq)を用いた以外は、実施例2と同様にしてシール剤を得た。 [Comparative Example 5]
(A) A sealant was obtained in the same manner as in Example 2, except that 2-ethylhexyl phosphate (oxygen atom equivalent: 81 g / eq) was used instead of trimellitic acid as the organic acid.
(D)遮光剤として、カーボン(MA-100R)の代わりに、カーボン(東海カーボン社製:#7350F、pH7.0、粒子径28nm)を用いた以外は、実施例1と同様にしてシール剤を得た。 [Comparative Example 6]
(D) A sealant was prepared in the same manner as in Example 1 except that carbon (# 7350F, pH 7.0, particle size 28 nm) was used as a light shielding agent instead of carbon (MA-100R). I got
(D)遮光剤として、カーボン(MA-100R)の代わりに、カーボン(三菱ケミカル社製:#2300、pH8.0、粒子径15nm)を用いた以外は、実施例1と同様にしてシール剤を得た。 [Comparative Example 7]
(D) A sealant similar to that of Example 1 except that carbon (Mitsubishi Chemical Corporation: # 2300, pH 8.0, particle size 15 nm) was used instead of carbon (MA-100R) as a light-shielding agent. I got
実施例および比較例で得られたシール剤について、次の評価を行った。 [Evaluation]
The following evaluations were performed on the sealants obtained in Examples and Comparative Examples.
シール剤をスパチュラで10μl程度採取し、25mm×45mm×厚さ5mmの無アルカリガラス上に滴下した。シールパターンは、直径5mmの円状とした。そして、対となる無アルカリガラスを重なるように貼りあわせ、治具で固定した。
治具で固定した試験片に対して、紫外線照射装置(ウシオ電機社製)から、500mW/cm2の紫外線(波長365nm)を照射し、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3.0J/cm2とした。光によって硬化させた試験片を、オーブンを用いて120℃、60分加熱処理し、黒色度測定用のサンプルとした。
紫外可視分光光度計(島津製作所社製、UV-2550)を使用して、シール部材(シール剤の硬化物)の透過率(%T)を測定した。そして、波長500nmにおける透過率(%T)を用いて、黒色度(OD値)を「OD値=-log(%T/100)」により濃度換算して算出した。 <Blackness>
About 10 μl of the sealing agent was collected with a spatula, and dropped on a 25 mm × 45 mm × 5 mm thick non-alkali glass. The seal pattern was a circle having a diameter of 5 mm. Then, a pair of non-alkali glass was stuck together so as to overlap, and fixed with a jig.
The test piece fixed with the jig was irradiated with ultraviolet light (wavelength 365 nm) of 500 mW / cm 2 from an ultraviolet irradiation device (manufactured by Ushio Inc.) to cure the sealant. At this time, the illuminance energy of the ultraviolet light was 3.0 J / cm 2 . The test piece cured by light was heated in an oven at 120 ° C. for 60 minutes to obtain a sample for measuring blackness.
The transmittance (% T) of the seal member (cured sealant) was measured using an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation). Then, using the transmittance (% T) at a wavelength of 500 nm, the blackness (OD value) was calculated by converting the density into "OD value = -log (% T / 100)".
シール剤をスパチュラで10μl程度採取し、25mm×45mm×厚さ5mmの無アルカリガラス上に滴下した。シールパターンは、直径5mmの円状とした。そして、対となる無アルカリガラスを重なるように貼りあわせ、治具で固定した。
治具で固定した試験片に対して、紫外線照射装置(ウシオ電機社製)から、500mW/cm2の紫外線(波長365nm)を照射し、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3.0J/cm2とした。光によって硬化させた試験片を、オーブンを用いて120℃、60分加熱処理し、分散性評価用のサンプルとした。
このサンプルを顕微鏡で観察し、視野2mm×2mmのなかに存在する異物(遮光剤の凝集物)の数をカウントした。
○:異物なし
△:異物10個未満
×:異物10個以上 <Dispersibility>
About 10 μl of the sealing agent was collected with a spatula, and dropped on a 25 mm × 45 mm × 5 mm thick non-alkali glass. The seal pattern was a circle having a diameter of 5 mm. Then, a pair of non-alkali glass was stuck together so as to overlap, and fixed with a jig.
The test piece fixed with the jig was irradiated with ultraviolet light (wavelength 365 nm) of 500 mW / cm 2 from an ultraviolet irradiation device (manufactured by Ushio Inc.) to cure the sealant. At this time, the illuminance energy of the ultraviolet light was 3.0 J / cm 2 . The test piece cured by light was heated in an oven at 120 ° C. for 60 minutes to obtain a sample for dispersibility evaluation.
This sample was observed with a microscope, and the number of foreign substances (aggregates of light-shielding agents) present in a visual field of 2 mm × 2 mm was counted.
○: No foreign matter △: Less than 10 foreign matters ×: 10 or more foreign matters
実施例および比較例で得られたシール剤を、ディスペンサー(武蔵エンジニアリング製 ショットマスター)を用いて、透明電極と配向膜が予め形成された40mm×45mmガラス基板(EHC社製 RT-DM88-PIN)上に、外寸35mm×40mmの四角形の枠状(メインシール)に、貼り合せ後の線幅が0.7mm(断面積3500μm2)となるように塗布した。またその外周に外寸38mm×43mmの四角形の枠状に、貼り合せ後の線幅が1.0mmとなるようにシール剤を塗布した。
次いで、基板貼り合せ後のパネル内容量に相当する量の液晶材料(MLC-7021-00メルク社製)を、メインシールの枠内にディスペンサーを用いて精密に滴下した。対になるガラス基板を減圧下で貼り合せた後、大気開放して貼り合わせた。その後、メインシールの下半分を覆うようにブラックマトリクスがライン/スペース=300μm/100μmで形成された基板で遮光した状態で、1000mJ/cm2の光(波長365nmセンサーで校正した光)を照射し、さらに120℃で1時間加熱した。
遮光シール剤を硬化処理した後の液晶表示パネルについて、以下のように評価した。
○:液晶漏れが発生していない
△:液晶漏れは発生していないが、シール剤に液晶が差し込んでいる状態
×:液晶漏れが発生した <Evaluation of photocurability (liquid crystal leak)>
Using a dispenser (Musashi Engineering Shotmaster), a 40 mm × 45 mm glass substrate (RT-DM88-PIN manufactured by EHC) on which a transparent electrode and an alignment film have been formed in advance using the sealants obtained in the examples and comparative examples. It was applied on a rectangular frame (main seal) having an outer size of 35 mm × 40 mm so that the line width after bonding was 0.7 mm (cross-sectional area: 3500 μm 2 ). Further, a sealant was applied to the outer periphery in a square frame shape having an outer size of 38 mm × 43 mm so that the line width after bonding was 1.0 mm.
Next, a liquid crystal material (manufactured by MLC-7021-00 Merck Co., Ltd.) corresponding to the capacity of the panel after bonding the substrates was precisely dropped into the frame of the main seal using a dispenser. After bonding the glass substrates to be paired under reduced pressure, they were opened to the atmosphere and bonded. Thereafter, light of 1000 mJ / cm 2 (light calibrated by a sensor having a wavelength of 365 nm) is irradiated in a state where the black matrix is covered with a substrate formed with a line / space of 300 μm / 100 μm so as to cover the lower half of the main seal. And further heated at 120 ° C. for 1 hour.
The liquid crystal display panel after the hardening treatment of the light shielding sealant was evaluated as follows.
:: No liquid crystal leakage occurred Δ: No liquid crystal leakage occurred, but liquid crystal was inserted into sealant ×: Liquid crystal leakage occurred
スクリーン版を使用してシール剤を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。
治具で固定した試験片に対して、紫外線照射装置(ウシオ電機社製)で、500mW/cm2の紫外線(波長365nm)を照射し、遮光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3.0J/cm2とした。光によって遮光シール剤を硬化させた試験片を、オーブンを用いて120℃、60分加熱処理し、接着強度測定用のサンプルとした。
引張試験機(インテスコ社製)を用いて、引張速度を2mm/分とし、硬化した遮光シール剤をガラス底面に対して平行な方向に引き剥がすことにより、平面の引張強度を測定した。ここで、接着強度は、平面引張強度の大きさに応じて4段階で以下のように評価した。
◎:引張強度が15MPa以上
〇:引張強度が10MPa以上15MPa未満
×:引張強度が10MPa未満 <Evaluation of photocurability (adhesive strength)>
The sealant was printed on a 25 mm × 45 mm × 5 mm thick non-alkali glass using a screen plate. The seal pattern was a circle having a diameter of 1 mm. Then, they were mounted on a pair of non-alkali glass in a seal pattern and fixed with a jig.
The test piece fixed by the jig was irradiated with an ultraviolet ray (wavelength: 365 nm) of 500 mW / cm 2 by an ultraviolet ray irradiation device (manufactured by Ushio Inc.) to cure the light-shielding sealant. At this time, the illuminance energy of the ultraviolet rays was 3.0 J / cm 2 . The test piece obtained by curing the light-shielding sealant with light was heated at 120 ° C. for 60 minutes using an oven to obtain a sample for measuring the adhesive strength.
Using a tensile tester (manufactured by Intesco Corporation), the tensile speed was set to 2 mm / min, and the cured light-shielding sealant was peeled off in a direction parallel to the glass bottom surface to measure the tensile strength in a plane. Here, the adhesive strength was evaluated in the following four stages according to the magnitude of the plane tensile strength.
◎: Tensile strength of 15 MPa or more 〇: Tensile strength of 10 MPa or more and less than 15 MPa ×: Tensile strength of less than 10 MPa
実施例および比較例で得られた0.1gのシール剤と、1gの液晶(MLC-7021-000、メルク社製)とをバイアル瓶に投入し、120℃で1時間加熱して液晶混合物を得た。次いで、この液晶混合物を取り出して、透明電極が予め形成されたガラスセル(KSSZ-10/B111M1NSS05、EHC社製)に注入し、電圧1Vを印加し、60Hzでの電圧保持率を6254型測定装置(東陽テクニカ製)により測定した。評価は以下のように行った。
〇:電圧保持率が90%以上であった場合(液晶への汚染が少ない)
×:電圧保持率が90%未満であった場合(液晶への汚染が生じた) <Liquid crystal contamination (voltage holding ratio)>
0.1 g of the sealant obtained in each of Examples and Comparative Examples and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck) were charged into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture. Obtained. Next, the liquid crystal mixture is taken out, injected into a glass cell (KSS-10 / B111M1NSS05, manufactured by EHC) on which a transparent electrode is formed in advance, a voltage of 1 V is applied, and a voltage holding ratio at 60 Hz is measured by a 6254 type measuring device. (Manufactured by Toyo Technica). The evaluation was performed as follows.
〇: When the voltage holding ratio is 90% or more (contamination to the liquid crystal is small)
×: When the voltage holding ratio was less than 90% (contamination of the liquid crystal occurred).
ディスペンス用シリンジに、実施例および比較例で得られた10gのシール剤を入れ、脱泡処理を行った。脱法処理後のシール剤2gを使用して初期粘度を測定した。また、このシール剤を23℃、50%RH、イエロールーム下で1週間保存し、保存後の粘度を測定した。各粘度は、E型回転型粘度計(BROOKFIELD社製、デジタルレオメータ型式DV-III ULTRA)を使用して測定した。具体的には、シール剤を25℃で5分間放置した後、半径12mm、角度3°のCP-52型コーンプレート型センサーを用いて、回転数2.5rpmで測定した。得られた値から、安定性(粘度安定性)を、以下のように評価した。
○(優れる):初期粘度に対する1週間後の粘度の割合(上昇率)が1.2倍以下であった
△(やや優れる):初期粘度に対する1週間後の粘度の割合(上昇率)が1.2を超えて、1.5倍以下であった
×(劣る):初期粘度に対する1週間後の粘度の割合(上昇率)が1.5倍を超えた <Stability evaluation>
Into a syringe for dispensing, 10 g of the sealant obtained in each of Examples and Comparative Examples was placed, and defoaming treatment was performed. The initial viscosity was measured using 2 g of the sealant after the de-treatment. The sealant was stored at 23 ° C., 50% RH under a yellow room for one week, and the viscosity after storage was measured. The respective viscosities were measured using an E-type rotary viscometer (manufactured by BROOKFIELD, digital rheometer model DV-III ULTRA). Specifically, after leaving the sealant at 25 ° C. for 5 minutes, the measurement was performed at a rotation speed of 2.5 rpm using a CP-52 cone-plate sensor having a radius of 12 mm and an angle of 3 °. From the obtained values, the stability (viscosity stability) was evaluated as follows.
((Excellent): The ratio of the viscosity after one week to the initial viscosity (increase rate) was 1.2 times or less. Δ (somewhat excellent): The ratio of the viscosity after one week to the initial viscosity (increase rate) was 1 X: less than 1.5 times × (poor): The ratio of the viscosity after one week to the initial viscosity (increase rate) exceeded 1.5 times
Claims (10)
- (A)有機酸と、
(B)1分子内にエチレン性不飽和二重結合を少なくとも1つ有する光硬化性樹脂(ただし、前記(A)有機酸を除く)と、
(C)チタノセン系光重合開始剤と、
(D)pHが7.0未満またはpHが8.0を超える遮光剤と、
(E)1分子内にエポキシ基を少なくとも1つ有する熱硬化性化合物(ただし、前記(B)光硬化性樹脂を除く)と、
(F)熱硬化剤と、
を含み、
前記(A)有機酸の下記式(1)で表される酸素原子当量が、23g/eq以上75g/eq以下である、液晶滴下工法用遮光シール剤。
酸素原子当量(g/eq)=(有機酸の分子量)/(有機酸1分子中の酸素原子数)・・(1) (A) an organic acid;
(B) a photocurable resin having at least one ethylenically unsaturated double bond in one molecule (however, excluding the (A) organic acid);
(C) a titanocene-based photopolymerization initiator;
(D) a light-shielding agent having a pH of less than 7.0 or a pH of more than 8.0,
(E) a thermosetting compound having at least one epoxy group in one molecule (however, excluding the (B) photocurable resin);
(F) a thermosetting agent,
Including
(A) A light-shielding sealant for a liquid crystal dropping method, wherein the organic acid has an oxygen atom equivalent represented by the following formula (1) of 23 g / eq or more and 75 g / eq or less.
Oxygen atom equivalent (g / eq) = (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1) - 黒色度が2~5である、
請求項1に記載の液晶滴下工法用遮光シール剤。 Blackness is 2 to 5,
The light-shielding sealant for a liquid crystal dropping method according to claim 1. - 前記(D)遮光剤が炭素およびチタンのうち、少なくとも一方を含む、
請求項1または2に記載の液晶滴下工法用遮光シール剤。 (D) the light-shielding agent contains at least one of carbon and titanium,
The light-shielding sealant for a liquid crystal dropping method according to claim 1. - 前記(A)有機酸が1分子内に、-OH基、-NH2基、-NHR基(Rは、芳香族、脂肪族炭化水素又はこれらの誘導体を表す)、-COOH基、-OP(=O)(OH)2基、-P(=O)(OH)2基、-SO3H基、-CONH2基、および-NHOH基からなる群より選ばれる官能基を少なくとも1つ有する、
請求項1~3のいずれか一項に記載の液晶滴下工法用遮光シール剤。 (A) In one molecule of the organic acid, an —OH group, a —NH 2 group, a —NHR group (R represents an aromatic or an aliphatic hydrocarbon or a derivative thereof), a —COOH group, and —OP ( = O) (OH) 2 groups, —P (= O) (OH) 2 groups, —SO 3 H groups, —CONH 2 groups, and —NHOH groups, having at least one functional group.
The light-shielding sealant for a liquid crystal dropping method according to any one of claims 1 to 3. - 前記(B)光硬化性樹脂が分子内にエポキシ基をさらに有する、
請求項1~4のいずれか一項に記載の液晶滴下工法用遮光シール剤。 (B) the photocurable resin further has an epoxy group in the molecule,
The light-shielding sealant for a liquid crystal dropping method according to any one of claims 1 to 4. - 前記(F)熱硬化剤が、ジヒドラジド系熱潜在性硬化剤、イミダゾール系熱潜在性硬化剤、アミンアダクト系熱潜在性硬化剤、およびポリアミン系熱潜在性硬化剤からなる群より選ばれる1以上である、
請求項1~5のいずれか一項に記載の液晶滴下工法用遮光シール剤。 (F) at least one selected from the group consisting of a dihydrazide heat latent curing agent, an imidazole heat latent curing agent, an amine adduct heat latent curing agent, and a polyamine heat latent curing agent. Is,
The light-blocking sealant for a liquid crystal dropping method according to any one of claims 1 to 5. - 請求項1~6のいずれか一項に記載の液晶滴下工法用遮光シール剤を用いて、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、前記シールパターンの領域内、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、前記シールパターンを介して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。 A step of forming a seal pattern on one of the substrates using the light-shielding sealant for a liquid crystal dropping method according to any one of claims 1 to 6,
In the uncured state of the seal pattern, in the region of the seal pattern, or a step of dropping liquid crystal on the other substrate paired with the one substrate,
Superimposing the one substrate and the other substrate via the seal pattern,
Curing the seal pattern,
A method for manufacturing a liquid crystal display panel, comprising: - 前記シールパターンを硬化させる工程は、前記シールパターンに光を照射して前記シールパターンを硬化させる工程を含む、
請求項7に記載の液晶表示パネルの製造方法。 Curing the seal pattern includes irradiating the seal pattern with light to cure the seal pattern.
A method for manufacturing a liquid crystal display panel according to claim 7. - 前記シールパターンに照射する光は、可視光領域の光を含む、
請求項8に記載の液晶表示パネルの製造方法。 The light applied to the seal pattern includes light in a visible light region,
A method for manufacturing a liquid crystal display panel according to claim 8. - 前記シールパターンを硬化させる工程は、光が照射された前記シールパターンを加熱して硬化させる工程をさらに含む、
請求項8または9に記載の液晶表示パネルの製造方法。
The step of curing the seal pattern further includes a step of heating and curing the seal pattern irradiated with light,
A method for manufacturing a liquid crystal display panel according to claim 8.
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