CN114280853A - Sealant for liquid crystal packaging and preparation method thereof - Google Patents
Sealant for liquid crystal packaging and preparation method thereof Download PDFInfo
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- CN114280853A CN114280853A CN202111596431.5A CN202111596431A CN114280853A CN 114280853 A CN114280853 A CN 114280853A CN 202111596431 A CN202111596431 A CN 202111596431A CN 114280853 A CN114280853 A CN 114280853A
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Abstract
The invention discloses a sealant for liquid crystal packaging and a preparation method thereof, relating to the field of photopolymerization initiators and having the technical scheme key points that: the liquid crystal composite material comprises curable resin, a thermal curing agent, a free radical polymerization inhibitor, a silane coupling agent, a filler and a macromolecular photoinitiator B, and the macromolecular photoinitiator B has the characteristics of low migration speed due to large molecular weight and large volume, and is not easy to pollute liquid crystal.
Description
Technical Field
The invention relates to the field of photopolymerization initiators, in particular to a sealant for liquid crystal packaging with low liquid crystal pollution and a preparation method thereof.
Background
In recent years, liquid crystal display units have been applied to large display screens of televisions and the like, and their use is being made for many purposes and demand is increasing, and therefore, for the manufacture of liquid crystal panels, in order to improve mass productivity, an odf (one Drop fill) system (also referred to as a liquid crystal dropping system or the like) has become the mainstream in place of a liquid crystal injection system, and in a dropping process, first, a rectangular seal pattern is formed by dispensing on one of 2 transparent substrates with electrodes, then, minute liquid crystal drops are dropped in a state where the sealant is not cured into the entire frame of the transparent substrates, the other transparent substrate is immediately superimposed, and the seal is irradiated with light such as ultraviolet rays to perform temporary curing, and thereafter, heating is performed at the time of liquid product annealing to perform main curing, thereby manufacturing a liquid crystal display element.
However, in recent years, the sealing position tends to be closer to the display pixel due to the demand for narrowing the side, and therefore, the electric characteristics of the display pixel portion tend to be affected by contamination from the sealant, and a display defect tends to be easily caused.
Chinese patent No. CN105900003B, a sealant for liquid crystal dropping method, a vertical conduction material and a liquid crystal display element, however, in recent years, due to the narrow bezel design of the panel, the sealant is very close to the display region, and a sealant of epoxy (meth) acrylate having 3 or more functions is used, in the one drop process, the sealant is easily dissolved into the liquid crystal to cause contamination when it comes into contact with the liquid crystal, and in the conventional ODF process, the liquid crystal sealant comes into contact with the liquid crystal in an uncured state, and therefore, the components of the sealant are easily dissolved out to cause contamination of the liquid crystal, in the sealing agent, the pollution of the photoinitiator component to the liquid crystal is particularly prominent because the conventional sealing agent generally adopts a small-molecule photoinitiator, and the residual small-molecule photoinitiator or photolysis product after ultraviolet curing migrates to the surface of the coating due to the fast migration speed and further dissolves in the liquid crystal to cause pollution.
Disclosure of Invention
The invention aims to provide a sealant for liquid crystal packaging and a preparation method thereof, because the sealant contains a macromolecular photoinitiator B, the macromolecular photoinitiator B has the characteristics of large molecular weight, large volume and slow migration speed, and is not easy to pollute liquid crystals, and in addition, because the macromolecular photopolymerization initiator compound of the resin has large polarity and poor compatibility with the liquid crystals, even if the macromolecular photoinitiator B contacts the liquid crystals in the liquid crystal dropping process, the liquid crystals cannot be polluted.
The technical purpose of the invention is realized by the following technical scheme: the sealant for liquid crystal packaging comprises curable resin, a thermal curing agent, a free radical polymerization inhibitor, a silane coupling agent, a filler and a macromolecular photoinitiator B, wherein the macromolecular photoinitiator B has the following structural formula:
y represents H or CH 3;
m and n represent integers of 0-2;
r1 represents CH2, (CH3)2C, (CH3) CH, O, S, SO 2;
r2 represents a moiety derived from a polybasic acid or a cyclic acid anhydride, and represents an aliphatic chain or aromatic compound structure having 1 to 20 carbon atoms;
r3 represents H, CH3,
Benzyl, phenethyl, phenylpropyl;
r4 represents CH3, CH3CH2,
Preferably, the curable resin contains one or a mixture of two of an epoxy resin, a (meth) acrylic acid modified resin, and a partially methacrylic acid modified bisphenol a type epoxy resin.
Preferably, the curable resin is used in an amount of 30 to 90 parts by weight based on the sealant composition, the resin-type photopolymerization initiator is used in an amount of 0.1 to 15 parts by weight, the radical polymerization inhibitor is used in an amount of 0.1 to 5 parts by weight, the thermal curing agent is used in an amount of 1 to 40 parts by weight, the filler is used in an amount of 5 to 60 parts by weight, and the silane coupling agent is used in an amount of 0.1 to 15 parts by weight.
Preferably, the free radical polymerization inhibitor comprises one or more of 2, 6-di-tert-butylcresol, butylated hydroxyanisole, 2, 6-di-tert-butyl-4-ethylphenol, stearoyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2' -methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 4' -thiobis-3-methyl-6-tert-butylphenol), 4-butylidenebis (3-methyl-6-tert-butylphenol), hydroquinone, p-methoxyphenol, or mixtures thereof.
Preferably, the thermal curing agent comprises one or more of organic acid hydrazide, imidazole derivatives, amine compounds, polyphenol compounds and acid anhydride.
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.
Preferably, the silane coupling agent comprises one or more of 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-isocyanatopropyltrimethoxysilane.
Preferably, the sealant further contains a UV photo radical polymerization initiator, and the UV photo radical polymerization initiator includes one or a mixture of more of benzophenone series compounds, acetophenone series compounds, acylphosphine oxide series compounds, titanocene series compounds, oxime ester series compounds, benzoin ether series compounds and thioxanthone series compounds.
The invention also aims to provide a preparation method of the sealant for liquid crystal packaging, which comprises the following steps: comprises the following steps:
the first step is as follows: the hydroxy ketone compound reacts with polybasic acid or cyclic acid anhydride to generate a compound A, the compound A reacts with a compound with at least 2 epoxy groups to generate a compound B, and the structure of the compound A is shown as follows:
r2 represents a moiety derived from a polybasic acid or a cyclic acid anhydride, and represents an aliphatic chain or aromatic compound structure having 1 to 20 carbon atoms;
r3 represents H, CH3,
Benzyl, phenethyl, phenylpropyl;
r4 represents CH3, CH3CH2,
The second step is that: pre-mixing (methyl) acrylic acid modified resin, partial methacrylic acid modified bisphenol A epoxy resin and macromolecular resin photopolymerization initiator B by using a planetary mixer, adding a thermal curing agent, a filler, a silane coupling agent and a free radical polymerization inhibitor, and mixing again;
the third step: grinding and mixing the components by a three-roller machine to prepare the sealant for liquid crystal packaging.
In conclusion, the invention achieves the following beneficial effects: firstly, the macromolecular resin photopolymerization initiator B is contained, so that the macromolecular resin photopolymerization initiator B has the characteristics of large molecular weight, large volume and low migration speed, and is not easy to pollute liquid crystals;
secondly, in addition, because the polarity of the macromolecular photoinitiator B compound is large, the macromolecular photoinitiator B compound has poor compatibility with liquid crystal, and even if the macromolecular photoinitiator B contacts the liquid crystal in a liquid crystal dropping process, the liquid crystal is not polluted.
Thirdly, the cleavage product of the macromolecular photoinitiator B is a part of the curable resin and can be cured cooperatively with the curable resin, so that liquid crystal is hardly polluted, and the cleavage product is a resin component which has a similar structure with the main resin and shows good intersolubility, and also shows more excellent adhesive property when in use.
Detailed Description
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
A preparation method of a sealant for liquid crystal packaging comprises the following steps: comprises the following steps:
the first step is as follows: the hydroxy ketone compound reacts with polybasic acid or cyclic acid anhydride to generate a compound A, the compound A reacts with a compound with at least 2 epoxy groups to generate a compound B, and the structure of the compound A is shown as follows:
r2 represents a moiety derived from a polybasic acid or a cyclic acid anhydride, and represents an aliphatic chain or aromatic compound structure having 1 to 20 carbon atoms;
r3 represents H, CH3,
Benzyl, phenethyl, phenylpropyl;
r4 represents CH3, CH3CH2,
The second step is that: pre-mixing the curable resin and the macromolecular resin photopolymerization initiator B by using a planetary mixer, and then adding a thermal curing agent, a filler, a silane coupling agent and a free radical polymerization inhibitor for mixing again;
the third step: grinding and mixing the components by a three-roller machine to prepare the sealant for liquid crystal packaging.
Examples of commercially available products of the above hydroxyketone compound include a photoinitiator 1173, a photoinitiator 184, a photoinitiator 2959, and benzil ketone, and preferably, the photoinitiator 184; examples of the polybasic acid-based compound include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and glutaric acid and adipic acid are preferable; examples of the above cyclic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, 1, 2-cyclohexanedicarboxylic anhydride, and phthalic anhydride, and succinic anhydride and phthalic anhydride are preferable.
Examples of the above epoxy resin having at least two epoxy groups include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2' -diallylbisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, propylene oxide-converted bisphenol a type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyhydric alcohol type epoxy resin, rubber-modified epoxy resin, glycidyl ester compound and the like, and bisphenol a type epoxy resin is preferable.
The curable resin comprises one or a mixture of two of epoxy resin, (methyl) acrylic acid modified resin and partial methacrylic acid modified bisphenol A epoxy resin; as the curable epoxy resin, known resins can be used, and examples thereof include bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, phenol novolac type epoxy resins, cresol novolac epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type resins, glycidyl amine type epoxy resins, heterocyclic epoxy resins, urethane-modified epoxy resins, and the like; the (meth) acrylic acid-modified resin is obtained by reacting (meth) acrylic acid with an epoxy compound, and is not particularly limited, and examples thereof include compounds obtained by reacting an epoxy resin with (meth) acrylic acid in the presence of a basic catalyst by a conventional method.
The epoxy resin used for synthesizing the resin photopolymerization initiator and the (meth) acrylic acid-modified resin is not particularly limited, and commercially available products include, for example: YD-128 (national chemical industry), NPEL-128 (south Asia), EPICLON 850 (Dielan), and jER828EL (Mitsubishi chemical corporation). Bisphenol F type epoxy resins such as EPICOAT806 and EPICOAT4004 (both manufactured by japan epoxy resin corporation); bisphenol S type epoxy resins such as EPICLON EXA1514 (available from DIC); 2,2' -diallylbisphenol A type epoxy resins such as RE-810NM (manufactured by Nippon chemical Co., Ltd.); hydrogenated bisphenol epoxy resins such as EPICLON EXA7015 (available from DIC Co., Ltd.), and propylene oxide-added bisphenol A epoxy resins such as EP-4000S (available from ADEKA Co., Ltd.); resorcinol type epoxy resins such as EX-201 (manufactured by Nagase Chemtex Co., Ltd.); biphenyl type epoxy resins such as EPICOAT YX-4000H (manufactured by epoxy resins Co., Ltd.); sulfide type epoxy resins such as YSLV-50TE (manufactured by Tokyo chemical Co., Ltd.); ether type epoxy resins such as YSLV-8ODE (manufactured by Tokyo chemical Co., Ltd.); dicyclopentadiene type epoxy resins such as EP-4088S (manufactured by ADEKA Co., Ltd.); naphthalene type epoxy resins such as EPICLONHP4032 and EPICLON EXA-4700 (both DIC Co., Ltd.); phenol novolac type epoxy resins such as EPICLON-770 (available from DIC corporation); o-cresol novolak type epoxy resins such as EPICLON-670-EXP-S (DIC Co., Ltd.); dicyclopentadiene novolak type epoxy resins such as EPICLON HP7200 (manufactured by DIC Co., Ltd.), and bisphenol novolak type epoxy resins such as NC-3000P (manufactured by Nippon Chemicals Co., Ltd.); a naphthol novolac type epoxy resin such as ESN-165S (manufactured by Tokyo chemical Co., Ltd.), a glycidyl amine type epoxy resin such as EPICOAT 630 (manufactured by Nippon epoxy resin Co., Ltd.), EPICLON 430 (manufactured by DIC Co., Ltd.), and TETRAD-X (manufactured by Mitsubishi gas chemical Co., Ltd.); alkyl polyol type epoxy resins such as ZX-1542 (manufactured by Tokyo chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Co., Ltd.), EPOLIGHT80MFA (manufactured by Kyoto chemical Co., Ltd.), DENACOL EX-611 (manufactured by Nagase Chemtex Co., Ltd.); and glycidyl ester compounds such as DENACOLEX-147(Nagase Chemtex).
Further, examples of commercially available products of the (meth) acrylic modified resin include: EBECRYL3700, EBECRYL3600, EBECRYL 3701, EBECRYL 3703, EBECRYL-3200, EBECRYL3201, EBECRYL3600, EBECRYL3702, EBECRYLL 3412, EBECRYL860, EBECRYL RDX 63182, EBECRYL 6040, EBECRYL. 3800 (both manufactured by Daicel cytec Co., Ltd.), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD, EMA-1020 (both manufactured by Nakamura chemical industries Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 7OPA, epoxy ester 20OPA, epoxy ester 8OMFA, epoxy ester 3002M, epoxy ester 3002A, epoxy ester 1600A, epoxy ester 3000M, epoxy ester 3000A, epoxy ester 20OEA, epoxy ester 40OEA (both manufactured by Kyoeisha Co., Ltd.), DENACOL acrylate DA-141, DENACOL acrylate DA-314, DEOL acrylate DA-91l (both manufactured by Nagase Chemtex Co., Ltd.), and the like.
Examples of commercially available products of the photo radical polymerization initiator include IRGACURE 184, IRGACURE369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXEO1, and Lucirin TPO (both manufactured by BASF); NCI-930 (manufactured by ADEKA corporation); SPEEDCURE EMK (manufactured by Japan Siber Hegner), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo chemical Co., Ltd.), and the like.
The macromolecular resin photopolymerization initiator B1-8 in the first step is prepared as follows:
(Synthesis of macromolecular resin photopolymerization initiator B1-1)
10g succinic anhydride, 19.9g photoinitiator 184 and 100ml DMF (N, N-dimethylformamide) are added into a 250ml three-neck flask, the temperature is raised to 120 ℃ under the stirring and nitrogen protection for reaction, the reaction is carried out until the acid value is constant to obtain A1-1, A1-1 is dropwise added into the three-neck flask filled with 60.03g bisphenol A epoxy resin within 2h under the stirring, the reaction is carried out until the acid value is constant, 50.2g compound B1-1 is obtained after the treatment, and the yield is 80%.
(Synthesis of macromolecular resin photopolymerization initiator B1-2)
12.55g of succinic anhydride, 20g of a photoinitiator 1173 and 100ml of DMF (N, N-dimethylformamide) are added into a 250ml three-neck flask, the temperature is raised to 120 ℃ under the stirring and nitrogen protection for reaction, the reaction is carried out until the acid value is constant, A1-2 is obtained, A1-2 is dropwise added into the three-neck flask filled with 74.63g of bisphenol A epoxy resin within 2h under the stirring, the reaction is carried out until the acid value is constant, 62.6g of a compound B1-2 is obtained through treatment, and the yield is 85%.
(Synthesis of macromolecular resin photopolymerization initiator B1-3)
9.19g of succinic anhydride, 20g of photoinitiator 2959 and 100ml of DMF (N, N-dimethylformamide) are added into a 250ml three-neck flask, the temperature is raised to 120 ℃ under the stirring and nitrogen protection for reaction, the reaction is carried out until the acid value is constant, A1-3 is obtained, A1-3 is dropwise added into the three-neck flask filled with 54.65g of bisphenol A epoxy resin within 2h under the stirring, the reaction is carried out until the acid value is constant, 50.38g of compound B1-1 is obtained through treatment, and the yield is 85%.
(Synthesis of macromolecular resin photopolymerization initiator B1-4)
9.71g of succinic anhydride, 20g of benzil ketone and 100ml of DMF (N, N-dimethylformamide) are added into a 250ml three-neck flask, the temperature is raised to 120 ℃ under the stirring and nitrogen protection for reaction, the reaction is carried out until the acid value is constant, A1-4 is obtained, A1-4 is dropwise added into the three-neck flask filled with 57.74g of bisphenol A epoxy resin within 2h under the stirring, the reaction is carried out until the acid value is constant, 49.208g of compound B1-4 is obtained after the treatment, and the yield is 80%.
(Synthesis of macromolecular resin photopolymerization initiator B1-5)
14.94g of phthalic anhydride, 20g of photoinitiator 184 and 100ml of DMF (N, N-dimethylformamide) are added into a 250ml three-neck flask, the temperature is raised to 120 ℃ under the stirring and nitrogen protection for reaction, the reaction is carried out until the acid value is constant to obtain A1-5, A1-5 is dropwise added into the three-neck flask filled with 59.99g of bisphenol A epoxy resin within 2h under the stirring, the reaction is carried out until the acid value is constant, 54.264g of compound B1-5 is obtained after the treatment, and the yield is 80%.
(Synthesis of macromolecular resin photopolymerization initiator B1-6)
18.58g of phthalic anhydride, 20g of photoinitiator 1173 and 100ml of DMF (N, N-dimethylformamide) are added into a 250ml three-neck flask, the temperature is raised to 120 ℃ under the stirring and nitrogen protection for reaction, the reaction is carried out until the acid value is constant, A1-6 is obtained, A1-6 is dropwise added into a three-neck flask filled with 74.63g of bisphenol A epoxy resin within 2h under the stirring, the reaction is carried out until the acid value is constant, 63.6g of compound B1-6 is obtained through treatment, and the yield is 80%.
(Synthesis of macromolecular resin photopolymerization initiator B1-7)
13.61g of phthalic anhydride, 20g of photoinitiator 2959 and 100ml of DMF (N, N-dimethylformamide) are added into a 250ml three-neck flask, the temperature is raised to 120 ℃ under the stirring and nitrogen protection for reaction, the reaction is carried out until the acid value is constant to obtain A1-7, A1-7 is dropwise added into a three-neck flask filled with 54.65g of bisphenol A epoxy resin within 2h under the stirring, the reaction is carried out until the acid value is constant, 50.856g of compound B1-7 is obtained after the treatment, and the yield is 80%.
(Synthesis of macromolecular resin photopolymerization initiator B1-8)
14.38g of phthalic anhydride, 20g of benzil ketone and 100ml of DMF (N, N-dimethylformamide) are added into a 250ml three-neck flask, the temperature is raised to 120 ℃ under the stirring and nitrogen protection for reaction, the reaction is carried out until the acid value is constant, A1-8 is obtained, A1-8 is dropwise added into the three-neck flask filled with 57.74g of bisphenol A epoxy resin within 2h under the stirring, the reaction is carried out until the acid value is constant, 52.824g of compound B1-8 is obtained after the treatment, and the yield is 80%.
(embodiment one)
A bisphenol A type epoxy resin (NPEL-128, south Asia) in an amount of 70 parts by weight, a (meth) acrylic acid modified resin (EBECRYL 3700 DIC) in an amount of 20 parts by weight, a part of a methacrylic acid modified bisphenol A type epoxy resin (UVAC 1561) in an amount of 10 parts by weight, and 2 parts by weight of compound B1-1 were previously mixed by a planetary mixer, and then 15 parts by weight of a heat-curing agent UDH-J, 15 parts by weight of an organic filler F351(ZEON Chemicals), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 1 part by weight of 2, 6-di-t-butyl-p-cresol were mixed again, and finally, the mixture was milled and mixed by a three-roll mill to prepare the sealant for liquid crystal encapsulation of example one.
(second embodiment)
A bisphenol A type epoxy resin (NPEL-128, south Asia) in an amount of 70 parts by weight, a (meth) acrylic acid modified resin (EBECRYL 3700 DIC) in an amount of 20 parts by weight, a part of a methacrylic acid modified bisphenol A type epoxy resin (UVAC 1561) in an amount of 10 parts by weight, and 2 parts by weight of compound B1-2 were previously mixed by a planetary mixer, and then 15 parts by weight of a heat-curing agent UDH-J, 15 parts by weight of an organic filler F351(ZEON Chemicals), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 1 part by weight of 2, 6-di-t-butyl-p-cresol were mixed again, and finally, the mixture was milled and mixed by a three-roll mill to prepare the sealant for liquid crystal encapsulation of example two.
(third embodiment)
A liquid crystal sealing material of example III was prepared by premixing 70 parts by weight of a bisphenol A type epoxy resin ("NPEL-128") (20 parts by weight of a (meth) acrylic acid-modified resin ("EBECRYL 3700" DIC Co., Ltd.), 10 parts by weight of a partial methacrylic acid-modified bisphenol A type epoxy resin ("UVAC 1561") and 2 parts by weight of compound B1-3 with a planetary mixer, adding 15 parts by weight of a heat-curing agent UDH-J, 15 parts by weight of an organic filler F351(ZEON chemical Co., Ltd.), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane and 1 part by weight of 2, 6-di-t-butyl-p-cresol, and grinding and mixing the mixture with a three-roll mill.
(example four)
A bisphenol A type epoxy resin (NPEL-128, south Asia) in an amount of 70 parts by weight, a (meth) acrylic acid modified resin (EBECRYL 3700 DIC) in an amount of 20 parts by weight, a part of a methacrylic acid modified bisphenol A type epoxy resin (UVAC 1561) in an amount of 10 parts by weight, and 2 parts by weight of compound B1-4 were previously mixed by a planetary mixer, and then 15 parts by weight of a heat-curing agent UDH-J, 15 parts by weight of an organic filler F351(ZEON Chemicals), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 1 part by weight of 2, 6-di-t-butyl-p-cresol were mixed again, and finally, the mixture was milled and mixed by a three-roll mill to prepare a sealant for liquid crystal encapsulation of example IV.
(fifth embodiment)
A bisphenol A type epoxy resin (NPEL-128, south Asia) in an amount of 70 parts by weight, a (meth) acrylic acid modified resin (EBECRYL 3700 DIC) in an amount of 20 parts by weight, a part of a methacrylic acid modified bisphenol A type epoxy resin (UVAC 1561) in an amount of 10 parts by weight, and 2 parts by weight of compound B1-5 were previously mixed by a planetary mixer, and then 15 parts by weight of a heat-curing agent UDH-J, 15 parts by weight of an organic filler F351(ZEON Chemicals), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 1 part by weight of 2, 6-di-t-butyl-p-cresol were mixed again, and finally, the mixture was milled and mixed by a three-roll mill to prepare the sealant for liquid crystal encapsulation of example five.
(sixth embodiment)
A liquid crystal sealing material of example six was prepared by premixing 70 parts by weight of a bisphenol A type epoxy resin ("NPEL-128") (20 parts by weight of a (meth) acrylic acid-modified resin ("EBECRYL 3700" DIC Co., Ltd.), 10 parts by weight of a partial methacrylic acid-modified bisphenol A type epoxy resin ("UVAC 1561") and 2 parts by weight of compound B1-6 with a planetary mixer, adding 15 parts by weight of a heat-curing agent UDH-J, 15 parts by weight of an organic filler F351(ZEON chemical Co., Ltd.), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane and 1 part by weight of 2, 6-di-t-butyl-p-cresol, and grinding and mixing the mixture with a three-roll mill.
(seventh embodiment)
A liquid crystal sealing material of example seven was prepared by premixing 70 parts by weight of a bisphenol A type epoxy resin ("NPEL-128") and 20 parts by weight of a (meth) acrylic acid-modified resin ("EBECRYL 3700", DIC Co., Ltd.), 10 parts by weight of a partial methacrylic acid-modified bisphenol A type epoxy resin ("UVAC 1561") and 2 parts by weight of compound B1-7 with a planetary mixer, further mixing 15 parts by weight of a heat-curing agent UDH-J, 15 parts by weight of an organic filler F351(ZEON chemical Co., Ltd.), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane and 1 part by weight of 2, 6-di-t-butyl-p-cresol, and finally grinding and mixing the mixture with a three-roll mill.
(eighth embodiment)
A bisphenol A type epoxy resin (NPEL-128, south Asia) in an amount of 70 parts by weight, a (meth) acrylic acid modified resin (EBECRYL 3700 DIC) in an amount of 20 parts by weight, a part of a methacrylic acid modified bisphenol A type epoxy resin (UVAC 1561) in an amount of 10 parts by weight, and 2 parts by weight of compound B1-8 were previously mixed by a planetary mixer, and then 15 parts by weight of a heat-curing agent UDH-J, 15 parts by weight of an organic filler F351(ZEON Chemicals), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 1 part by weight of 2, 6-di-t-butyl-p-cresol were mixed again, and finally, the mixture was milled and mixed by a three-roll mill to prepare the sealant for liquid crystal encapsulation of example eight.
(comparative example 1)
A liquid crystal sealing material was prepared by premixing 70 parts by weight of bisphenol A type epoxy resin ("NPEL-128") in south Asia, (20 parts by weight of (meth) acrylic modified resin ("EBECRYL 3700" DIC Co.), 10 parts by weight of partial methacrylic modified bisphenol A type epoxy resin ("UVAC 1561") and 2 parts by weight of photoinitiator 184 with a planetary mixer, further mixing 15 parts by weight of thermal curing agent UDH-J, 15 parts by weight of organic filler F351(ZEON Co., Ltd.), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane and 1 part by weight of 2, 6-di-t-butyl-p-cresol, and finally grinding and mixing the mixture with a three-roll mill.
(comparative example two)
A liquid crystal sealing material of two-part type was prepared by premixing 70 parts by weight of a bisphenol A type epoxy resin ("NPEL-128") in south Asia, (20 parts by weight of a (meth) acrylic acid-modified resin ("EBECRYL 3700" DIC Co., Ltd.), 10 parts by weight of a partial methacrylic acid-modified bisphenol A type epoxy resin ("UVAC 1561") and 2 parts by weight of a photoinitiator 2959 with a planetary mixer, further mixing 15 parts by weight of a heat-curing agent UDH-J, 15 parts by weight of an organic filler F351(ZEON Co., Ltd.), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane and 1 part by weight of 2, 6-di-t-butyl-p-cresol with a three-roll mill, and finally mixing them by grinding with a three-roll mill.
(comparative example III)
A liquid crystal sealing material was prepared by mixing 70 parts by weight of bisphenol A type epoxy resin (NPEL-128, south Asia), 20 parts by weight of (meth) acrylic acid modified resin ("EBECRYL 3700", DIC Co.), 10 parts by weight of partial methacrylic acid modified bisphenol A type epoxy resin ("UVAC 1561"), and 2 parts by weight of photoinitiator TPO (2,4, 6-trimethylbenzoyldiphenylphosphine oxide) in advance with a planetary mixer, adding 15 parts by weight of a heat-curing agent UDH-J, 15 parts by weight of an organic filler F351(ZEON chemical Co., Ltd.), 15 parts by weight of silica, 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 1 part by weight of 2, 6-di-t-butyl-p-cresol in a mixer, and grinding and mixing them with a three-roll mill.
Evaluation of
The following viscosity stability, (meth) acryloyl group reaction rate, liquid crystal contamination, and adhesion evaluation were performed on the liquid crystal sealing sealants of examples and comparative examples, and the results are shown in Table 1-1 (viscosity stability)
For the liquid crystal sealing sealants of examples and comparative examples, the viscosity change at 25 ℃ before and after seven days (2.5rpm test) was measured by an E-type viscometer, and the viscosity stability was expressed as the ratio of the viscosity after seven days (2.5rpm at 25 ℃) to the initial viscosity (2.5rpm at 25 ℃). A ratio of less than 1.1 indicates excellent viscosity stability, a ratio of between 1.1 and 1.2 indicates good viscosity stability, and a ratio of greater than 1.2 indicates poor viscosity stability.
((meth) acryloyl group reaction Rate)
The sealants of examples and comparative examples were applied to a glass substrate to form a sealant having a thickness of 0.5mm, and the sealant was irradiated with an ultraviolet irradiation device at an illuminance of 100mW/cm2 for 30 seconds to prepare a sample for a curing test, and the reactivity of acryloyl groups was measured by an FT-IR analysis method. The reactivity of acryloyl groups was calculated from the peak area of acryloyl groups in the obtained IR spectrum. For the calculation of the reaction rate, the decrease in the area of the absorption peak of acryloyl group (in the vicinity of 1630 cm-1) was calculated based on the area of the absorption peak of benzene ring double bond (in the vicinity of 1500 cm-1). When the reaction rate of acryloyl is less than 50%, the reaction rate is poor, when the reaction rate is between 50% and 70%, the reaction rate is general, and when the reaction rate is more than 70%, the reaction is excellent.
(liquid Crystal contamination-Ni Point Change)
0.1g of the sealant in each of the above examples and comparative examples was added to a penicillin bottle, 1g of liquid crystal (TN, SLC13T50L01, manufactured by SLC) was further added to the bottle, and then the bottle was put into an oven at 120 ℃ for 1 hour, and after returning to room temperature, the upper liquid crystal portion was taken out, and a sample was prepared by filtration with a 0.2um filter, and measurement was carried out by a differential scanning calorimeter (DSC, manufactured by TA, USA) at a temperature rise of 10 ℃/min. The change in the Ni (liquid crystal phase transition point) value was observed in comparison with the initial liquid crystal. The Ni content was within 1 ℃ and the fouling property was evaluated as excellent, and the Ni content was between 1 and 1.5 ℃ and the fouling property was evaluated as general. The Ni value decreased by more than 1.5 ℃, and the fouling was evaluated as poor.
(adhesiveness)
And (3) point-coating the sealant in the embodiment and the comparative example between two pieces of ITO glass or ITO glass coated with an alignment film, extruding and attaching under pressure, keeping the diameter of a glue point after attaching at 1.5mm, irradiating for 30s at the illumination intensity of 100mW/cm2 by using an ultraviolet irradiation device, and heating for 60min at 120 ℃ to cure the glue frame so as to obtain the adhesive test piece. The adhesive strength of the obtained adhesive test piece was measured by using a tensiometer. The adhesiveness was evaluated by "x" when the adhesive strength was 300N/cm2 or more, by "O" when the adhesive strength was 270N/cm2 or more and less than 300N/cm2, and by "x" when the adhesive strength was less than 270N/cm 2.
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 (9)
1. The sealant for liquid crystal packaging is characterized by comprising curable resin, a thermal curing agent, a free radical polymerization inhibitor, a silane coupling agent, a filler and a macromolecular photoinitiator B, wherein the macromolecular photoinitiator B has the following structural formula:
y represents H or CH3；
m and n represent integers of 0-2;
r1 represents CH2、(CH3)2C、(CH3)CH、O、S、SO2；
R2 represents a moiety derived from a polybasic acid or a cyclic acid anhydride, and represents an aliphatic chain or aromatic compound structure having 1 to 20 carbon atoms;
r3 represents H, CH3、
Benzyl, phenethyl, phenylpropyl;
r4 represents CH3、CH3CH2、
2. The sealing agent for liquid crystal package according to claim 1, wherein: the curable resin comprises one or a mixture of two of epoxy resin, (methyl) acrylic acid modified resin and partial methacrylic acid modified bisphenol A epoxy resin.
3. The sealing agent for liquid crystal package according to claim 1, wherein: the curable resin is 30-90 parts by weight of the sealant composition, the resin type macromolecular photopolymerization initiator is 0.1-15 parts by weight, the free radical polymerization inhibitor is 0.1-5 parts by weight, the thermal curing agent is 1-40 parts by weight, the filler is 5-60 parts by weight, and the silane coupling agent is 0.1-15 parts by weight.
4. The sealing agent for liquid crystal package according to claim 1, wherein: the free radical polymerization inhibitor comprises one or more of 2, 6-di-tert-butyl cresol, butylated hydroxyanisole, 2, 6-di-tert-butyl-4-ethylphenol, stearoyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2' -methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 4' -thiobis-3-methyl-6-tert-butylphenol), 4-butylidenebis (3-methyl-6-tert-butylphenol), hydroquinone and p-methoxyphenol.
5. The sealing agent for liquid crystal package according to claim 1, wherein: the thermal curing agent comprises one or more of organic acid hydrazide, imidazole derivatives, amine compounds, polyphenol compounds and acid anhydride.
6. The sealing agent for liquid crystal package 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. The sealing agent for liquid crystal package according to claim 1, wherein: the silane coupling agent comprises one or more of 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-isocyanate propyltrimethoxysilane.
8. The sealing agent for liquid crystal package according to claim 1, wherein: the sealant also contains a UV photo-free radical polymerization initiator, wherein the UV photo-free radical polymerization initiator comprises one or a mixture of more of benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds and thioxanthone compounds.
9. A method for manufacturing the sealant according to claim 1, comprising the steps of:
the first step is as follows: the hydroxy ketone compound reacts with polybasic acid or cyclic acid anhydride to generate a compound A, the compound A reacts with a compound with at least 2 epoxy groups to generate a compound B, and the structure of the compound A is shown as follows:
r2 represents a moiety derived from a polybasic acid or a cyclic acid anhydride, and represents an aliphatic chain or aromatic compound structure having 1 to 20 carbon atoms;
r3 represents H, CH3,
Benzyl, phenethyl, phenylpropyl;
r4 represents CH3, CH3CH2,
The second step is that: pre-mixing (methyl) acrylic acid modified resin, partial methacrylic acid modified bisphenol A epoxy resin and macromolecular resin photopolymerization initiator B by using a planetary mixer, adding a thermal curing agent, a filler, a silane coupling agent and a free radical polymerization inhibitor, and mixing again;
the third step: grinding and mixing the components by a three-roller machine to prepare the sealant for liquid crystal packaging.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111596431.5A CN114280853A (en) | 2021-12-24 | 2021-12-24 | Sealant for liquid crystal packaging and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111596431.5A CN114280853A (en) | 2021-12-24 | 2021-12-24 | Sealant for liquid crystal packaging and preparation method thereof |
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| CN202111596431.5A Pending CN114280853A (en) | 2021-12-24 | 2021-12-24 | Sealant for liquid crystal packaging and preparation method thereof |
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| Country | Link |
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| CN (1) | CN114280853A (en) |
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2021
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