CN114384727A - Sealing frame adhesive for liquid crystal panel and preparation method thereof - Google Patents
Sealing frame adhesive for liquid crystal panel and preparation method thereof Download PDFInfo
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- CN114384727A CN114384727A CN202111596101.6A CN202111596101A CN114384727A CN 114384727 A CN114384727 A CN 114384727A CN 202111596101 A CN202111596101 A CN 202111596101A CN 114384727 A CN114384727 A CN 114384727A
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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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13398—Spacer materials; Spacer properties
Abstract
The invention discloses a sealing frame adhesive of a liquid crystal panel and a preparation method thereof, relating to the field of sealing frame adhesives, and the technical scheme is as follows: the curing agent is an adduct consisting of a hydrazide compound (A) and an epoxy compound (B) or an acid or anhydride compound (C), and compared with the original curing agent, the curing agent adduct reduces primary amine in the curing agent, avoids the sealant from reacting, such as Schiff base reaction and Michael addition reaction, avoids the deterioration of the storage stability of the resin, and ensures that the frame sealant has excellent storage stability and curing property.
Description
Technical Field
The invention relates to the field of sealing frame glue, in particular to sealing frame glue of a liquid crystal panel and a preparation method thereof.
Background
In recent years, in order to improve production efficiency and to use liquid crystal in a large quantity, the manufacturing method of a liquid crystal panel display element is gradually changed from the conventional vacuum injection method to the liquid crystal dropping method. Liquid crystal dropping process: a circle of sealant is coated on a transparent substrate with electrodes to form a rectangular sealing pattern, then a certain amount of liquid crystal is dripped into a sealing frame of the substrate before the sealant is cured, and the two transparent substrates with electrodes are jointed in a vacuum state. Then, the sealant is irradiated by UV for temporary curing, and finally, the liquid crystal is annealed for main curing. In the liquid crystal dropping method, in view of rapid curing, a radical polymerization reactive compound having an epoxy acrylate compound as a main component is currently used in many cases as a liquid crystal sealing agent.
With the popularization of smartphones, tablet terminals, and the like, there is an increasing demand for small liquid crystal panels, and since a liquid crystal dropping place is close to a sealing frame, liquid crystal is in contact with an uncured sealant for a long time after attachment until UV irradiation, and thus there is a problem of contamination of the liquid crystal and the uncured sealant. In addition, the flexible liquid crystal display which is light in weight, safe and can be freely bent gradually expands in the market. Many conventional sealants are relatively rigid cured products and are suitable for bonding substrates such as glass having a small amount of deformation. In the case of a flexible display, the substrate may be peeled off or broken due to a change in shape of the substrate.
Chinese patent publication No. CN101484844A discloses a liquid crystal sealing agent and a liquid crystal display unit using the same, wherein the curing agent component used is a hydrazide compound such as adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide and Amicure VDH (manufactured by Ajinomoto Fine-chemical company, Inc.), which reacts not only with an epoxy group but also with a (meth) acryloyl group under heating. Among the above hydrazides, the hydrazide compound reacts not only with an epoxy group under heating but also with a (meth) acryloyl group, and these compounds cause a change in viscosity or the like with time at room temperature, which makes the storage stability of the product poor.
Disclosure of Invention
The invention aims to provide a sealing frame adhesive of a liquid crystal panel, wherein a curing agent adduct reduces primary amine in a curing agent compared with an original curing agent, the reaction of the sealing adhesive, such as Schiff base reaction and Michael addition reaction, is avoided, the deterioration of the storage stability of resin is avoided, and the storage stability and the curing property of the frame adhesive are excellent.
The technical purpose of the invention is realized by the following technical scheme: the sealing frame adhesive of the liquid crystal panel comprises a curable resin, a curing agent, a filler and a photoinitiator, wherein the curing agent is an adduct consisting of a hydrazide compound (A) and an epoxy compound (B) or an acid or anhydride compound (C), and the structural formula of the curing agent is as follows:
preferably, the hydrazide compound (A) comprises one or more of adipic Acid Dihydrazide (ADH), sebacic acid dihydrazide (SDH), isophthalic acid dihydrazide (IDH), dodecanedicarboxylic acid dihydrazide (DDH), salicyloyl hydrazide (SAH), 7, 11-octadecadienyl-1, 18-dicarbonyl dihydrazide (UDH), 1, 3-bis (hydrazinocarboethyl) 5-isopropylhydantoin (VDH), octadecane-1, 18-dicarboxylic acid dihydrazide (LDH).
Preferably, the epoxy compound (B) comprises one or more of resorcinol diglycidyl ether, 1, 4-butanediol glycidyl ether and cester glycidyl ether, alkylene glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, C12-14 fatty glycidyl ether, benzyl glycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether and allyl glycidyl ether.
Preferably, the acid or acid anhydride compound (C) comprises one or more of hexahydrophthalic acid, benzoic acid, pyromellitic dianhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, tetrabromophthalic anhydride, maleic anhydride, 70# anhydride, 647# anhydride, 308 elaeostearic anhydride.
Preferably, the curable resin includes epoxy acrylate UVACURE 1561.
Preferably, the filler comprises one or more mixtures of talc, asbestos, silica, diatomaceous earth, smectite (smectite), bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles.
The invention also aims to provide a preparation method of the sealant for liquid crystal packaging, which comprises the following steps:
firstly, adding a hydrazide compound (A) and toluene into a three-neck flask provided with a stirrer, a dropping funnel and a condenser, and stirring and dissolving at 80-100 ℃; cooling to 25 ℃ and dripping a mixed solution consisting of an epoxy compound (B), an acid or anhydride compound (C) and toluene within 1 h; keeping the temperature for 1h, detecting the epoxy value, distilling the solvent toluene under reduced pressure when the epoxy value is reduced to 0.02eq/100g, and carrying out filter pressing by a filter press to obtain a curing agent, wherein the structural formula of the curing agent obtained by the addition reaction of part of primary amine of a hydrazide compound (A) and an epoxy compound (B) is (a), and the reaction equation is (1); the structural formula of the curing agent obtained by the addition reaction of all primary amines of the hydrazide compound (A) and the epoxy compound (B) is (B), and the reaction formulas are respectively (2); the structural formula of the curing agent obtained by addition reaction of partial primary amine of the hydrazide compound (A) and the acid or anhydride compound (C) is (d), and the reaction formulas are respectively (3); the structural formula of the curing agent obtained by the addition reaction of all primary amines of the hydrazide compound (A) and the acid or anhydride compound (C) is (e), and the reaction formulas are (4);
secondly, adding a filler and a photoinitiator into the curable resin in a double-planet stirrer, stirring for 20 minutes in vacuum, adding the curing agent obtained in the first step after the temperature is reduced to 25 ℃, and stirring for 20 minutes in vacuum again; and finally, obtaining the frame glue product through a three-roller grinding machine and a filter press.
In conclusion, the invention achieves the following beneficial effects: compared with the original curing agent, the curing agent adduct reduces primary amine in the curing agent, avoids the deterioration of the storage stability of the resin caused by Schiff base reaction of the sealant, and has excellent storage stability and curing property.
Detailed Description
The present invention will be described in further detail below.
The sealing frame adhesive of the liquid crystal panel comprises curable resin, a curing agent, a filler and a photoinitiator, wherein the curing agent is an adduct consisting of a hydrazide compound (A) and an epoxy compound (B) or an acid or anhydride compound (C), and the structural formula of the curing agent is as follows:
wherein R is1~R3Is any group such as alkane, alkene, aromatic hydrocarbon, heterocycle, etc.
The preparation method of the sealing frame adhesive of the liquid crystal panel comprises the following steps:
firstly, adding a hydrazide compound (A) and toluene into a three-neck flask provided with a stirrer, a dropping funnel and a condenser, and stirring and dissolving at 80-100 ℃; cooling to 25 ℃ and dripping a mixed solution consisting of an epoxy compound (B), an acid or anhydride compound (C) and toluene within 1 h; keeping the temperature for 1h, detecting the epoxy value, distilling the solvent toluene under reduced pressure when the epoxy value is reduced to 0.02eq/100g, and carrying out filter pressing by a filter press to obtain a curing agent, wherein the structural formula of the curing agent obtained by the addition reaction of part of primary amine of a hydrazide compound (A) and an epoxy compound (B) is (a), and the reaction equation is (1); the structural formula of the curing agent obtained by the addition reaction of all primary amines of the hydrazide compound (A) and the epoxy compound (B) is (B), and the reaction formulas are respectively (2); the structural formula of the curing agent obtained by addition reaction of partial primary amine of the hydrazide compound (A) and the acid or anhydride compound (C) is (d), and the reaction formulas are respectively (3); the structural formula of the curing agent obtained by the addition reaction of all primary amines of the hydrazide compound (A) and the acid or anhydride compound (C) is (e), and the reaction formulas are (4);
secondly, adding a filler and a photoinitiator into the curable resin in a double-planet stirrer; stirring in vacuum for 20 minutes, adding the curing agent obtained in the first step after the temperature is reduced to 25 ℃, and stirring in vacuum for 20 minutes again; and finally, obtaining the frame glue product through a three-roller grinding machine and a filter press.
1-10 parts of curing agent is prepared by the method in the first step, and the method comprises the following steps:
curing agent 1
17g of ADH and 50g of toluene were charged in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and dissolved by stirring at 80 to 100 ℃. The temperature is reduced to 25 ℃, and a mixed solution of 21g of resorcinol diglycidyl ether and 50g of toluene is added dropwise within 1 h. Keeping the temperature for 1h, detecting the epoxy value, distilling the solvent toluene under reduced pressure when the epoxy value is reduced to 0.1eq/100g, and performing pressure filtration by a filter press to obtain an adduct compound curing agent slurry curing agent 1, wherein the reaction equation is shown as follows.
Curing agent 2
34g of ADH and 50g of toluene were charged in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and dissolved by stirring at 80 to 100 ℃. The temperature is reduced to 25 ℃, and a mixed solution of 21g of resorcinol diglycidyl ether and 50g of toluene is added dropwise within 1 h. Keeping the temperature for 1h, detecting the epoxy value, distilling the solvent toluene under reduced pressure when the epoxy value is reduced to 0.02eq/100g, and performing pressure filtration by a filter press to obtain an adduct compound curing agent slurry curing agent 2, wherein the reaction equation is shown as follows.
Curing agent 3
17g of ADH and 50g of toluene were charged in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and dissolved by stirring at 80 to 100 ℃. The temperature is reduced to 25 ℃, and a mixed solution of 15g of phenol glycidyl ether and 50g of toluene is added dropwise within 1 h. Keeping the temperature for 1h, detecting the epoxy value, distilling the solvent toluene under reduced pressure when the epoxy value is reduced to 0.02eq/100g, and performing pressure filtration by a filter press to obtain an adduct compound curing agent slurry curing agent 3, wherein the reaction equation is shown as follows.
Curing agent 4
17g of ADH and 50g of toluene were charged in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and dissolved by stirring at 80 to 100 ℃. The temperature is reduced to 25 ℃, and a mixed solution of 18g of 1, 4-butanediol diglycidyl ether and 50g of toluene is added dropwise within 1 hour. Keeping the temperature for 1h, detecting the epoxy value, distilling the solvent toluene under reduced pressure when the epoxy value is reduced to 0.07eq/100g, and performing pressure filtration by a filter press to obtain an adduct compound curing agent slurry curing agent 4, wherein the reaction equation is shown as follows.
Curing agent 5
17g of ADH and 50g of toluene were charged in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and dissolved by stirring at 80 to 100 ℃. The temperature is reduced to 25 ℃, and a mixed solution of 9g of 1, 4-butanediol diglycidyl ether and 50g of toluene is added dropwise within 1 hour. Keeping the temperature for 1h, detecting the epoxy value, distilling the solvent toluene under reduced pressure when the epoxy value is reduced to 0.02eq/100g, and performing pressure filtration by a filter press to obtain an adduct compound curing agent slurry curing agent 5, wherein the reaction equation is shown as follows.
Curing agent 6
17g of ADH and 50g of toluene were charged in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and dissolved by stirring at 80 to 100 ℃. The temperature is reduced to 25 ℃, and a mixed solution consisting of 15g of hexahydrophthalic acid and 50g of toluene is added dropwise within 1 hour. And (3) keeping the temperature for 1h, detecting an amine value, distilling the solvent toluene under reduced pressure when the amine value is reduced to 600mgKOH/g, and performing pressure filtration by using a filter press to obtain an adduct compound curing agent slurry curing agent 6, wherein the reaction equation is shown as follows.
Curing agent 7
21g of SDH and 50g of toluene were charged into a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and dissolved by stirring at 80 to 100 ℃. The temperature is reduced to 25 ℃, and a mixed solution consisting of 15g of hexahydrophthalic acid and 50g of toluene is added dropwise within 1 hour. And (3) keeping the temperature for 1h, detecting an amine value, distilling the solvent toluene under reduced pressure when the amine value is reduced to 500mgKOH/g, and performing pressure filtration by using a filter press to obtain an adduct compound curing agent slurry curing agent 7, wherein the reaction equation is shown as follows.
Curing agent 8
17g of ADH and 50g of toluene were charged in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and dissolved by stirring at 80 to 100 ℃. The temperature is reduced to 25 ℃, and a mixed solution consisting of 11g of benzoic acid and 50g of toluene is added dropwise within 1 h. And (3) keeping the temperature for 1h, detecting an amine value, distilling the solvent toluene under reduced pressure when the amine value is reduced to 700mgKOH/g, and performing pressure filtration by using a filter press to obtain an adduct compound curing agent slurry curing agent 8, wherein the reaction equation is shown as follows.
Curing agent 9
21g of SDH and 50g of toluene were charged into a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and dissolved by stirring at 80 to 100 ℃. The temperature is reduced to 25 ℃, and a mixed solution consisting of 11g of benzoic acid and 50g of toluene is added dropwise within 1 h. And (3) keeping the temperature for 1h, detecting an amine value, distilling the solvent toluene under reduced pressure when the amine value is reduced to 600mgKOH/g, and performing pressure filtration by using a filter press to obtain an adduct compound curing agent slurry curing agent 9, wherein the reaction equation is shown as follows.
Curing agent 10
17g of ADH and 50g of toluene were charged in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and dissolved by stirring at 80 to 100 ℃. The temperature is reduced to 25 ℃, and a mixed solution of 14g of the glycidyl ether and 50g of toluene is added dropwise within 1 h. Keeping the temperature for 1h, detecting the epoxy value, distilling the solvent toluene under reduced pressure when the epoxy value is reduced to 0.02eq/100g, and performing pressure filtration by a filter press to obtain the adduct compound curing agent slurry curing agent 10, wherein the reaction equation is shown as follows.
Example 1
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃, 28.6g of the above hydrazide adduct compound 1 was added and the mixture was again stirred under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Example 2
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃, 10.3g of the above hydrazide adduct 2 was added and the mixture was again stirred under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Example 3
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃, 24.1g of the above hydrazide adduct 3 was added and the mixture was again stirred under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Example 4
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃, 26.4g of the above hydrazide adduct 4 was added and the mixture was again stirred under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Example 5
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃, 9.8g of the above hydrazide adduct 5 was added and the mixture was again stirred under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Example 6
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃, 24.1g of the above hydrazide adduct compound 6 was added and the mixture was again stirred under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Example 7
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃, 29.0g of the above hydrazide adduct 7 was added and the mixture was again stirred under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Example 8
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃, 21.1g of the above hydrazide adduct 8 was added and the mixture was again stirred under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Example 9
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃, 25.8g of the above hydrazide adduct compound 9 was added and the mixture was again stirred under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Example 10
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃, 7.8g of the above hydrazide adduct 10 was added and the mixture was again stirred under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Comparative example 1
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 ℃ 9.6g of ADH were added, stirring again under vacuum for 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Comparative example 2
In a double planetary mixer, 100g of epoxy acrylate UVACURE 1561 was added 1g of silica filler, 1g of photoinitiator Iracure 651. After stirring under vacuum for 20 minutes and waiting for the temperature to drop to 25 deg.C, 16.5g of VDH was added and stirring under vacuum for another 20 minutes. And finally, grinding by a three-roller grinder and performing filter press to obtain the product.
Test method
Storage stability: the viscosity of the resin at 2.5rpm measured on a cone and plate viscometer with the resin thermostatted to 25 ℃ is recorded as the initial viscosity. The resin was stored in a thermostat at 25 ℃ for 1 week, and the cone plate viscosity was measured again to calculate the viscosity change rate for one week. The viscosity change was more than 50000cps and marked as X, less than 50000cps and more than 3000cps and marked as X, less than 30000cps and marked as excellent.
Curing property:
mixing resin with 1% spacer, coating in the middle of glass substrate, bonding, and performing 365nm integrated brightness 3000mJ/cm2The mixture is put into a constant temperature box and is kept at the temperature of 120 ℃ for 1 hour. Taking out the glue, and measuring the curing degree by an infrared spectrometer, wherein the curing degree is 915cm-1Is an epoxy group, 830cm-1As a reference peak. X is less than 80%, O is less than 90% and more than 80%, and O is more than 90%The% was recorded as. circleincircle.
As is clear from Table 1 below, the curing agents of examples 1 to 10 were excellent in storage stability and curability.
TABLE 1
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (7)
1. The frame sealing glue of the liquid crystal panel is characterized by comprising curable resin, a curing agent, a filler and a photoinitiator, wherein the curing agent is an adduct consisting of a hydrazide compound (A) and an epoxy compound (B) or an acid or anhydride compound (C), and the structural formula of the curing agent is as follows:
2. a sealant for a liquid crystal panel according to claim 1, wherein: the hydrazide compound (A) comprises one or more of adipic Acid Dihydrazide (ADH), sebacic acid dihydrazide (SDH), isophthalic acid dihydrazide (IDH), dodecane dicarboxylic acid dihydrazide (DDH), salicyloyl hydrazide (SAH), 7, 11-octadecadienyl-1, 18-dicarbonyl dihydrazide (UDH), 1, 3-bis (hydrazinocarboethyl) 5-isopropyl hydantoin (VDH), octadecane-1, 18-dicarboxylic acid dihydrazide (LDH).
3. A sealant for a liquid crystal panel according to claim 1, wherein: the epoxy compound (B) comprises one or more of resorcinol diglycidyl ether, 1, 4-butanediol glycidyl ether and cester glycidyl ether, alkylene glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, C12-14 fatty glycidyl ether, benzyl glycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether and allyl glycidyl ether.
4. A sealant for a liquid crystal panel according to claim 1, wherein: the acid or acid anhydride compound (C) comprises one or more of hexahydrophthalic acid, benzoic acid, pyromellitic dianhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, tetrabromophthalic anhydride, maleic anhydride, 70# anhydride, 647# anhydride and 308 elaeostearic anhydride.
5. A sealant for a liquid crystal panel according to claim 1, wherein: the curable resin comprises epoxy acrylate UVACURE 1561.
6. A sealant for a liquid crystal panel according to claim 1, wherein: the filler comprises one or more of talc, asbestos, silica, diatomaceous earth, smectite (smectite), bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles.
7. A method for manufacturing a sealant for a liquid crystal panel according to claim 1, comprising the steps of:
firstly, adding a hydrazide compound (A) and toluene into a three-neck flask provided with a stirrer, a dropping funnel and a condenser, and stirring and dissolving at 80-100 ℃; cooling to 25 ℃ and dripping a mixed solution consisting of an epoxy compound (B), an acid or anhydride compound (C) and toluene within 1 h; keeping the temperature for 1h, detecting the epoxy value, distilling the solvent toluene under reduced pressure when the epoxy value is reduced to 0.02eq/100g, and carrying out filter pressing by a filter press to obtain a curing agent, wherein the structural formula of the curing agent obtained by the addition reaction of part of primary amine of a hydrazide compound (A) and an epoxy compound (B) is (a), and the reaction equation is (1); the structural formula of the curing agent obtained by the addition reaction of all primary amines of the hydrazide compound (A) and the epoxy compound (B) is (B), and the reaction formulas are respectively (2); the structural formula of the curing agent obtained by addition reaction of partial primary amine of the hydrazide compound (A) and the acid or anhydride compound (C) is (d), and the reaction formulas are respectively (3); the structural formula of the curing agent obtained by the addition reaction of all primary amines of the hydrazide compound (A) and the acid or anhydride compound (C) is (e), and the reaction formulas are (4);
secondly, adding a filler and a photoinitiator into the curable resin in a double-planet stirrer, stirring for 20 minutes in vacuum, adding the curing agent obtained in the first step after the temperature is reduced to 25 ℃, and stirring for 20 minutes in vacuum again; and finally, obtaining the frame glue product through a three-roller grinding machine and a filter press.
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CN202111596101.6A CN114384727A (en) | 2021-12-24 | 2021-12-24 | Sealing frame adhesive for liquid crystal panel and preparation method thereof |
CN202211498846.3A CN115755469A (en) | 2021-12-24 | 2022-11-28 | Sealing frame adhesive for liquid crystal panel and preparation method thereof |
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CN202111596101.6A CN114384727A (en) | 2021-12-24 | 2021-12-24 | Sealing frame adhesive for liquid crystal panel and preparation method thereof |
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CN202111596101.6A Withdrawn CN114384727A (en) | 2021-12-24 | 2021-12-24 | Sealing frame adhesive for liquid crystal panel and preparation method thereof |
CN202211498846.3A Pending CN115755469A (en) | 2021-12-24 | 2022-11-28 | Sealing frame adhesive for liquid crystal panel and preparation method thereof |
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CN202211498846.3A Pending CN115755469A (en) | 2021-12-24 | 2022-11-28 | Sealing frame adhesive for liquid crystal panel and preparation method thereof |
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JP3043600B2 (en) * | 1995-07-20 | 2000-05-22 | 住友ベークライト株式会社 | Liquid crystal display element sealing material composition and liquid crystal display element using the same |
JPH11147935A (en) * | 1997-11-18 | 1999-06-02 | Ajinomoto Co Inc | Adhesive composition |
KR101228430B1 (en) * | 2002-11-06 | 2013-02-01 | 니폰 가야꾸 가부시끼가이샤 | Sealing material for liquid crystal and liquid crystal display cell using same |
CN101585929B (en) * | 2009-06-25 | 2012-08-08 | 嘉兴荣泰雷帕司绝缘材料有限公司 | Hydrazide latency improving curing agent and preparation method thereof |
CN109957209B (en) * | 2017-12-25 | 2021-08-17 | 北京科化新材料科技有限公司 | Epoxy resin composition, resin product, preparation method thereof and resin product |
CN112080239B (en) * | 2020-09-10 | 2023-02-17 | 苏州润邦半导体材料科技有限公司 | Sealant composition and preparation method and application thereof |
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2021
- 2021-12-24 CN CN202111596101.6A patent/CN114384727A/en not_active Withdrawn
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- 2022-11-28 CN CN202211498846.3A patent/CN115755469A/en active Pending
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