CN115286656A - Additive, preparation method thereof, alignment composition and display device - Google Patents
Additive, preparation method thereof, alignment composition and display device Download PDFInfo
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- CN115286656A CN115286656A CN202210937581.6A CN202210937581A CN115286656A CN 115286656 A CN115286656 A CN 115286656A CN 202210937581 A CN202210937581 A CN 202210937581A CN 115286656 A CN115286656 A CN 115286656A
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- 239000000654 additive Substances 0.000 title claims abstract description 57
- 230000000996 additive effect Effects 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 54
- 239000011521 glass Substances 0.000 claims description 38
- 229920001721 polyimide Polymers 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 239000004642 Polyimide Substances 0.000 claims description 27
- 125000003545 alkoxy group Chemical group 0.000 claims description 26
- 239000004973 liquid crystal related substance Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical group 0.000 claims description 4
- 229910018557 Si O Inorganic materials 0.000 claims description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 12
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 abstract description 11
- 230000003287 optical effect Effects 0.000 abstract description 10
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- 125000005376 alkyl siloxane group Chemical group 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical group [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 4
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical group [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 150000007523 nucleic acids Chemical class 0.000 description 2
- 102000039446 nucleic acids Human genes 0.000 description 2
- 108020004707 nucleic acids Proteins 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- 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
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Abstract
The application provides an additive and a preparation method thereof, an alignment composition and a display device, wherein acrylate and halogenated alkyl siloxane are reacted to generate the additive of a compound with a formula I, the formula I contains siloxane groups and acrylate groups, and the siloxane groups can be chemically bonded with silicon dioxide, so that the bonding performance of a material and a substrate containing silicon dioxide is enhanced, and the film forming quality of the material is improved; and the acrylate group has excellent optical transparency and toughness, and the polymer with a net structure is formed by curing and free radical polymerization of double bonds in the acrylate group through light initiation, so that the compactness of the material is improved, and the film forming quality of the material is further improved.
Description
Technical Field
The application relates to the technical field of display, in particular to an additive, a preparation method thereof, an alignment composition and a display device.
Background
Thin film transistor liquid crystal display (TFT-LCD) is still dominant in the display field, and as the number and demand of liquid crystal display product users increase, customers demand higher and higher various product performances, such as contrast, aperture ratio, power consumption, and the like. The TFT-LCD panel controls the electric field between the electrodes of the glass substrates through the switching function of the thin film transistors on the substrates, thereby controlling the director state of the liquid crystal layer between the substrates to change the light transmittance of the liquid crystal layer to realize display. In order to effectively control the liquid crystal, an alignment process must be included in the manufacturing process of the liquid crystal panel. Without the Polyimide (PI) alignment film, the liquid crystal molecules would be randomly aligned and the liquid crystal would not be deflected in the intended direction under the external electric field. As a first station of the box forming process, the film forming process of the polyimide alignment film is crucial, and various display properties of the product are directly affected. However, in the prior art, the organic polyimide alignment film and the inorganic substrate have poor adhesion, which affects the film forming quality.
Disclosure of Invention
The application provides an additive and a preparation method thereof, an alignment composition, a display device and a preparation method thereof, which can enhance the bonding performance between an alignment film material and a glass substrate and improve the film forming quality of the alignment film material.
In a first aspect, the present application provides an additive which is a compound having the formula I:
wherein Q is 1 Is represented by an alkyl group having 1 to 5 carbon atoms, R 1 、R 2 Each represents an alkoxy group having 1 to 5 carbon atoms, R 3 Is represented by carbonAn alkoxy group having 1 to 5 atoms or an alkyl group having 1 to 5 carbon atoms.
Optionally, in some embodiments herein, the compound is selected from:
In a second aspect of the present application, there is provided a method for preparing an additive, comprising:
reacting an acrylate salt of formula ii with a haloalkylsiloxane of formula iii to form an additive, said additive being a compound having formula I:
wherein Q is 1 Is represented by alkyl with 1-5 carbon atoms, R 1 、R 2 Each represents an alkoxy group having 1 to 5 carbon atoms, R 3 Represents an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms; the formula II is as follows:
The formula III is as follows:
Optionally, in some embodiments of the present application, in the step of reacting the acrylate of formula ii with the haloalkylsiloxane of formula iii to form the additive, the reaction temperature is 80 ℃ to 110 ℃, and the reaction time is 3.5h to 4.5h.
In a third aspect, the present application provides an alignment composition comprising: polyimide and an additive, such as the additive described above.
Optionally, in some embodiments of the present application, the mass percentage of the polyimide is 90% to 95%, and the mass percentage of the additive is 5% to 10%.
In a fourth aspect of the present application, there is provided a display device, which includes: the glass substrate, the alignment film and the liquid crystal layer are of a laminated structure, and the alignment film is prepared from the alignment composition. Optionally, in some embodiments of the present application, the thickness of the alignment film is 95nm to 110nm.
In a fifth aspect of the present application, there is provided a method for manufacturing a display device, including:
coating the alignment composition on a glass substrate, heating, and carrying out a crosslinking reaction on the alignment composition to generate a crosslinked product, wherein the crosslinked product is bonded with Si of the glass substrate through an Si-O bond;
polymerizing the cross-linked product by using the action of light to form a polymer with a net structure, namely forming an alignment film bonded with the glass substrate on the glass substrate;
and forming a liquid crystal layer on the alignment film to obtain the display device.
Alternatively, in some embodiments of the present application, in the step of spin-coating the alignment composition on the glass substrate and heating, the heating temperature is 190 ℃ to 240 ℃, and the heating time is 20min to 40min.
The application has at least one or more of the following benefits:
the additive with the formula I contains siloxane groups and acrylate groups, wherein the siloxane groups can be chemically bonded with silicon dioxide, so that the bonding property of a material and a substrate containing silicon dioxide can be enhanced, and the film forming quality of the material is improved; and double bonds in the acrylate groups undergo free radical polymerization through photo-initiation, and are rapidly cured to form a polymer with a net structure, so that the compactness of the material is improved, and the film forming quality of the material is further improved. The additive with the formula I combines siloxane groups and acrylate groups, utilizes the excellent optical transparency and toughness of the acrylate groups, and can enhance the bonding property between an organic material and an inorganic substrate and improve the film forming property of the organic material on the premise of not influencing the optical property of the material.
Drawings
Fig. 1 is a schematic view of a first structure of a display device provided in the present application;
fig. 2 is a schematic diagram of a second structure of the display device provided in the present application;
FIG. 3 is a schematic view of an alignment film manufacturing process according to an embodiment of the present disclosure;
FIG. 4 is a schematic view of a process for preparing an alignment film according to another embodiment of the present disclosure;
FIG. 5 is a schematic representation of a polyimide film (comparative example) under an OM optical microscope;
fig. 6 is a schematic representation of a polyimide alignment film with additives added under OM optical microscope.
The scores in the figure are indicated as: the liquid crystal display device comprises a display device 100, a glass substrate 101, a first alignment film (alignment film) 102, a liquid crystal layer 103, a second alignment film 104, a color film plate 105 and a cross-linked product 1021.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. Furthermore, it should be understood that the detailed description and specific examples, while indicating exemplary embodiments of the invention, are given by way of illustration and explanation only, and are not intended to limit the scope of the invention.
The present application provides an additive, a method of preparing the same, an alignment composition and a display device, which are described in detail below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments of the present application. In the following embodiments, the description of each embodiment has its own emphasis, and reference may be made to the related description of other embodiments for parts that are not described in detail in a certain embodiment.
Embodiments of the present application provide an additive that is a compound having formula I:
wherein Q is 1 Is represented by alkyl with 1-5 carbon atoms, R 1 、R 2 Each represents an alkoxy group having 1 to 5 carbon atoms, R 3 Is represented by an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms.
In some embodiments, when R 1 、R 2 Each represents an alkoxy group having 1 to 5 carbon atoms, R 3 Represents an alkyl group having 1 to 5 carbon atoms. In a specific example, R 1 、R 2 Each is represented by-OCH 3 ,R 3 Is represented by-CH 3 or-CH 2 CH 3 . In other embodiments, R 1 、R 2 And R 3 Each represents an alkoxy group having 1 to 5 carbon atoms. In a specific example, R 1 、R 2 And R 3 Each is represented by-OCH 3 。
In formula I above, siloxane groups are included, and such groups will thermally crosslink at high temperatures to form alternating Si-O bonds. The specific reaction mechanism is as follows:
wherein n is 16-2An integer of 0; the R1 'group and the R2' group are respectively alkyl with the carbon number of 1-5; r is 4 The group represents an alkyl group having 1 to 5 carbon atoms.
It should be noted that, referring to fig. 4, when the number of siloxane groups in formula I is 3, more alternate Si — O bonds are advantageously formed, so as to improve the adhesion between the material and the glass substrate (the main component of which is silicon dioxide), and at the same time, a network structure with higher interweaving density is advantageously formed, so as to improve the compactness of the material.
In the above formula I, an acrylic group is also included, and under UV light irradiation, a C = C double bond in the acrylic group may undergo radical polymerization. The specific reaction mechanism is as follows:
wherein the value of n is an integer of 16-20. Q 1 Is represented by an alkyl group having 1 to 5 carbon atoms.
In other embodiments of the present application, the compound having formula I is selected from:
In other embodiments of the present application, there is provided a method of preparing an additive, comprising:
reacting an acrylate of formula ii with a haloalkylsiloxane of formula iii to form an additive, the additive being a compound having the general formula I:
wherein Q is 1 Is represented by alkyl with 1-5 carbon atoms, R 1 、R 2 Each represents an alkoxy group having 1 to 5 carbon atoms, R 3 Is represented by an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms.
The formula II is:
The formula III is:
In one embodiment, the acrylate salt is potassium methacrylate and the haloalkylsiloxane is a chloroalkylsiloxane. In some embodiments, potassium methacrylate may be prepared using the following method:
a50% KOH (56.11g, 1mol) aqueous solution and 300mL of toluene were placed in a 1L four-necked flask equipped with a mechanical stirrer, a thermometer, a dropping funnel and a reflux condenser. Methacrylic acid (86.04g, 1mol) was slowly added from the dropping funnel with stirring. Subsequently, water was removed by azeotropic distillation, and about 250mL of toluene was removed by distillation, to obtain potassium methacrylate.
The reaction process for preparing potassium methacrylate is as follows:
the potassium methacrylate prepared in this example was used to synthesize the compound having formula I.
In one example, potassium methacrylate and chloroalkylsiloxane were used to synthesize the compound of formula I, as follows:
a mixed solution of 2.59g,10mmol of tetrabutylphosphonium chloride and 2.12g,5mmol of 4,4' -methylenebis (2, 6-di-t-butylphenol) in a mixture of 50mL of toluene, 20mL of ethyl methyl ketone and 1mol of the corresponding chloroalkylsiloxane was charged into a four-necked flask, and potassium methacrylate was further charged into the four-necked flask. The structural formula of the chloroalkylsiloxane is:
heating the suspension at 110 ℃ for 4h under stirring, filtering the generated potassium chloride, washing the potassium chloride with toluene, and separating the product by column distillation under reduced pressure to obtain the target product, wherein the structural formula of the target product is as follows:
the synthesis process of the target product is as follows:
The results of the nucleic acid resonance hydrogen spectrum of the target product are as follows:
1 H NMR(CDCl 3 ,400MHz):δ＝0.14(s,3H,SiCH 3 ),1.30(t,J＝8.4Hz,2H,SiCH 2 ),1.64(qui,J＝7.66Hz,2H,CH 2 ),1.83(s,3H,CH 3 ),3.30(s,6H,2OCH 3 ),4.03(t,J＝6.93Hz,2H,CH 2 O),5.58(s,1H,H(H)C＝),6.11(s,1H,H(H)C＝)； 29 Si NMR(C6D6,71.54MHz):δ＝3.00.
in another example, potassium methacrylate and chloroalkylsiloxane were used to synthesize the compound having formula I, as follows:
a solution of 2.59g,10mmol of tetrabutylphosphonium chloride and 2.12g,5mmol of 4,4' -methylenebis (2, 6-di-t-butylphenol) in a mixture of 50mL of toluene, 20mL of ethyl methyl ketone and 1mol of the corresponding chloroalkylsiloxane was added to the four-necked flask, and potassium methacrylate was further added to the four-necked flask. The structural formula of the chloroalkylsiloxane is:
heating the suspension at 110 ℃ for 4h under stirring, filtering the generated potassium chloride, washing with toluene, and separating the product by column distillation under reduced pressure to obtain the target product, wherein the target product has the structural formula:
the synthesis process of the target product is as follows:
The results of the nucleic acid resonance hydrogen spectrum of the target product are as follows:
1 H NMR(CDCl 3 ,400MHz):δ＝0.66(t,J＝8.43Hz,2H,SiCH 2 ),1.76(qui,J＝7.66Hz,2H,CH 2 ),1.91(s,3H,CH 3 ),3.55(s,9H,3OCH 3 ),4.09(t,J＝6.72Hz,2H,CH 2 O),5.52(s,1H,H(H)C＝),6.07(s,1H,H(H)C＝)； 29 Si NMR(C6D6,59.62MHz):δ＝42.71.
in some embodiments, the acrylate of formula II and the haloalkylsiloxane of formula III are reacted at a temperature of 80 ℃ to 110 ℃ for a time of 3.5 hours to 4.5 hours. By adopting the reaction conditions, the synthesis reaction rate can be improved, the conversion rate of the target product can be improved, and the side reaction can be avoided.
In other embodiments of the present disclosure, an alignment composition is provided, which may be applied to the preparation of an alignment film in a display device. The components of the alignment composition include: a polyimide and an additive, the additive being a compound having formula I:
wherein Q is 1 Is represented by alkyl with 1-5 carbon atoms, R 1 、R 2 Each represents an alkoxy group having 1 to 5 carbon atoms, R 3 Represents an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms.
The additive of the formula I contains acrylate groups with excellent optical transparency and toughness, and double bonds of the acrylate groups are subjected to photo-initiated free radical polymerization, so that a net structure is formed by rapid curing, the compactness of the material is further improved, and the film forming quality of the material is further improved. The formula I contains siloxane groups, and the siloxane groups can be chemically bonded with silicon dioxide components of a glass substrate of a display device, so that the bonding performance of the alignment composition and the glass substrate can be enhanced, and the film forming quality of film forming of the alignment composition is improved; in addition, the siloxane group and the acrylate group are combined, so that the bonding performance between the organic Polyimide (PI) material and the glass substrate is enhanced on the premise of not influencing the optical performance of the material, and the film forming compactness of the alignment composition is improved. Most of the additives commonly used in polyimide in the prior art only play a role of crosslinking polyimide molecules, but cannot be effectively combined with a glass substrate. The additive is used for improving the cohesiveness of the polyimide alignment film and the glass substrate, the compactness of the alignment film layer is improved, the film forming quality of the material is improved, and the method has the advantages of simplicity, effectiveness and low cost.
In other embodiments of the present disclosure, the polyimide is 90% to 95% by weight, and the additive is 5% to 10% by weight. The additive is mixed into the polyimide solution according to the mass ratio of 5-10%, so that the thermal crosslinking is favorably carried out on siloxane groups at the lower layer of the polyimide, si-O bonds are bonded with Si of the glass substrate, the chemical bonding is realized, and the adhesion between the alignment composition material and the glass substrate is enhanced; meanwhile, the method is favorable for generating the polyimide film with better compactness.
In other embodiments of the present application, a display device 100 is provided, referring to fig. 1, which includes: a glass substrate 101, an alignment film 102 and a liquid crystal layer 103 in a laminated structure, wherein the alignment film 102 is prepared by using an alignment composition. The alignment composition comprises: polyimide and an additive, wherein the mass ratio of the additive is 5% -10%, and the additive is a compound with a formula I:
wherein Q 1 Is represented by alkyl with 1-5 carbon atoms, R 1 、R 2 Each represents an alkoxy group having 1 to 5 carbon atoms, R 3 Is represented by an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms.
In another embodiment, a display device 100, please refer to fig. 2, which includes: the liquid crystal display device comprises a glass substrate 101, a first alignment film 102, a liquid crystal layer 103, a second alignment film 104 and a color film plate 105 which are of a laminated structure, wherein the first alignment film 102 is prepared from an alignment composition. The alignment composition comprises: polyimide and an additive, wherein the mass ratio of the additive is 5-10%, and the additive is a compound with a formula I:
wherein Q 1 Is represented by an alkyl group having 1 to 5 carbon atoms, R 1 、R 2 Each represents an alkoxy group having 1 to 5 carbon atoms, R 3 Is represented by an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms.
The additive is formed by organic-inorganic element hybridization, and is added as an additive of polyimide, so that the adhesiveness and compactness of the photo-alignment film can be improved, the film forming quality of the alignment film is improved on the premise of not influencing the optical performance, the effective control on liquid crystal is realized, and the display performance of a display device is improved.
In some embodiments, the display device adopts an alignment film with a thickness of 95nm-110nm, and the alignment film is formed by adding the additive with the formula I to improve the film forming quality of the alignment film, so that the effective control of the alignment film on liquid crystal is favorably improved, and the display performance of the display device is improved.
In other embodiments of the present application, there is provided a method of manufacturing a display device, including:
s01, coating the above alignment composition on a glass substrate, and heating to crosslink the alignment composition, thereby generating a crosslinked product, wherein the crosslinked product is bonded to Si of the glass substrate through Si — O bonds, and the reaction mechanism is as follows:
Referring to FIG. 3, a-1 is a schematic diagram of a cross-linking reaction between Si and two methoxy groups to form a cross-linked product.
S02, carrying out polymerization reaction on the cross-linked product by utilizing the illumination effect to form a polymer with a network structure, namely forming an alignment film bonded with the glass substrate on the glass substrate, wherein the reaction mechanism is as follows:
Referring to FIG. 3, a-2 is a schematic diagram of a polymer corresponding to the crosslinked product formed by a-1.
And S03, forming a liquid crystal layer on the alignment film to obtain the display device.
In other embodiments, when R 1 、R 2 And R 3 Each is represented by-OCH 3 The reaction mechanism is as follows:
The hydrolysis process is omitted from the schematic diagram of the above reaction mechanism.
Referring to FIG. 4, b-1 is a schematic view showing a cross-linked product formed by a cross-linking reaction of Si with three methoxy groups, and b-2 is a schematic view showing a polymer corresponding to the cross-linked product formed in b-1.
In some embodiments, the step of spin-coating the alignment composition on the glass substrate and heating is performed at a temperature of 190 ℃ to 240 ℃ for a time period of 20min to 40min. Is beneficial to fully generating crosslinking reaction so as to improve the crosslinking degree.
In one embodiment, a display device is prepared, comprising the steps of:
s1, adding 5% -10% of additive in mass percent into PI liquid to form an alignment composition, spin-coating the alignment composition on a 5 x 5cm ITO comb-shaped glass substrate, spin-coating the alignment composition on an ITO-free% substrate, pre-baking the alignment composition for 5min at 90 ℃, baking the alignment composition for 30min at 230 ℃, and performing thermal crosslinking on the additive of the alignment composition. Due to the interfacial effect, the crosslinked product is located under the PI film and adheres to the glass substrate. The film thickness of the obtained alignment film was about 100 nm.
S2, irradiating the glass substrates to 100mJ/cm 2 Irradiating with 254nm polarized ultraviolet for 5min to polymerize the side chain of the cross-linked product and form the polymer with network structure.
And S3, coating sealant on the surface of one ITO substrate, and assembling the ITO substrate with the other ITO substrate.
And S4, injecting liquid crystal in vacuum to prepare a liquid crystal box in horizontal alignment, thus obtaining the display device.
Test examples
1) The adhesion performance of the polyimide alignment film to which the additives of the above-described examples of the present application were added and the glass substrate was tested, while the polyimide film to which no additive was added was used as a control example.
The glass substrate adhered with the polyimide alignment film added with the additive and the glass substrate adhered with the polyimide film are simultaneously soaked in NMP, the glass substrate is completely peeled off after 25min, and the former still keeps an intact shape after 1 week, which is enough to prove that the additive provided by the application can obviously improve the adhesion between the polyimide alignment film and the glass substrate.
2) Referring to fig. 5, fig. 5 is a schematic diagram of a polyimide film (comparative example) under an OM optical microscope, which shows that the uniformity of the polyimide film is poor, indicating that the film forming quality is poor; referring to fig. 6, fig. 6 is a schematic diagram of a polyimide alignment film under an OM optical microscope with the additive of the above embodiment of the present application added thereto, which shows better uniformity and compactness, and illustrates that the film forming quality of the alignment film is improved after the additive is added.
The foregoing provides a detailed description of the present application, and the principles and embodiments of the present application are described herein using specific examples, which are provided only to help understand the method and the core concept of the present application; meanwhile, for a person skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (10)
1. An additive, characterized in that the additive is a compound having the formula I:
wherein Q 1 Is represented by an alkyl group having 1 to 5 carbon atoms, R 1 、R 2 Each represents an alkoxy group having 1 to 5 carbon atoms, R 3 Is represented by an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms.
2. Additive according to claim 1, characterized in that said compound is selected from:
3. A method of preparing an additive, comprising:
reacting an acrylate salt of formula ii with a haloalkylsiloxane of formula iii to form an additive, said additive being a compound having formula I:
wherein Q is 1 Is represented by alkyl with 1-5 carbon atoms, R 1 、R 2 Each represents an alkoxy group having 1 to 5 carbon atoms, R 3 Represents an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms; the formula II is as follows:
the formula III is as follows:
4. The method for preparing the additive according to claim 3, wherein in the step of reacting the acrylate of the formula II with the haloalkylsiloxane of the formula III to form the additive, the reaction temperature is 80 ℃ to 110 ℃, and the reaction time is 3.5h to 4.5h.
5. An alignment composition, comprising: polyimide and an additive as defined in any one of claims 1 to 2, or an additive produced by the production process as defined in any one of claims 3 to 4.
6. The alignment composition according to claim 5, wherein the polyimide is included in an amount of 90% to 95% by mass, and the additive is included in an amount of 5% to 10% by mass.
7. A display device, comprising: a glass substrate, an alignment film and a liquid crystal layer having a laminated structure, wherein the alignment film is prepared using the alignment composition according to any one of claims 5 to 6.
8. The display device according to claim 7, wherein the alignment film has a thickness of 95nm to 110nm.
9. A method of fabricating a display device, comprising:
applying the alignment composition according to any one of claims 5 to 6 on a glass substrate and heating to cause a cross-linking reaction of the alignment composition to generate a cross-linked product, the cross-linked product being bonded to Si of the glass substrate via Si-O bonds;
polymerizing the cross-linked product by using the action of light to form a polymer with a net structure, namely forming an alignment film bonded with the glass substrate on the glass substrate;
and forming a liquid crystal layer on the alignment film to obtain the display device.
10. The method of claim 9, wherein the step of spin coating the alignment composition on the glass substrate and heating is performed at a temperature of 190 ℃ to 240 ℃ for a time of 20min to 40min.
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