CN116396707A - Adhesive composition and preparation method and application thereof - Google Patents
Adhesive composition and preparation method and application thereof Download PDFInfo
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- CN116396707A CN116396707A CN202310487544.4A CN202310487544A CN116396707A CN 116396707 A CN116396707 A CN 116396707A CN 202310487544 A CN202310487544 A CN 202310487544A CN 116396707 A CN116396707 A CN 116396707A
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- adhesive composition
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- 239000000853 adhesive Substances 0.000 title claims abstract description 83
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 72
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 239000004593 Epoxy Substances 0.000 claims abstract description 32
- 125000000524 functional group Chemical group 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 21
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- MEVBAGCIOOTPLF-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CO1 MEVBAGCIOOTPLF-UHFFFAOYSA-N 0.000 claims description 3
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000003776 cleavage reaction Methods 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 230000007017 scission Effects 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 230000035515 penetration Effects 0.000 abstract description 7
- 239000003292 glue Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001723 curing Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Inorganic Chemistry (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, in particular to an adhesive composition, a preparation method and application thereof, wherein the adhesive composition comprises the following components: at least one resin contains epoxy functional groups which can be cured by heating, at least one resin contains acrylate groups which can be cured by UV light, at least one photoinitiator, at least one thermosetting agent which can react with the epoxy functional groups, a coupling agent and a modified filler; and (3) placing the filler in A-187 or KH550 for ultrasonic treatment and heating treatment, and drying to obtain the modified filler. The adhesive composition is applied to the preparation of liquid crystal display panels. The adhesive composition can meet the requirement of liquid crystal on less penetration of glue lines under the condition of coating lines with smaller line width, so that the problem of uneven images of a display panel is avoided, a stable and excellent display effect is shown, and the adhesive composition has higher bonding strength.
Description
Technical Field
The invention relates to an adhesive composition, a preparation method and application thereof, and belongs to the technical field of adhesives.
Background
The processing of electronic components often requires the use of an adhesive to assemble the components, and the gluing of many electronic components requires the ability to achieve dual curing, such as camera modules, panel packages, and the like. The UV rapid curing can provide rapid fixation in the early stage, and the final thermal curing can ensure the final bonding strength, ageing resistance and other performances.
The conventional method for manufacturing a display panel using the dual curing process is: firstly, coating a square frame on one side of a glass substrate by using an adhesive, then dripping liquid crystal in the frame, finally attaching the other side of the glass substrate in vacuum, performing UV pre-curing, and then performing thermal final curing; in the process, the liquid crystal enters the frame before UV pre-curing, at the moment, the adhesive is in a wet film state, the liquid crystal is easy to permeate into the adhesive in the vacuum lamination process, the permeation phenomenon is puncture, the greater the puncture depth is, the less stable and durable the product is, the display effect is deteriorated when the puncture depth is greater, and the problem of uneven display image is caused; the penetration depth of the liquid crystal to the frame glue can be observed under a microscope.
In the processing process of many electronic components at present, in order to display attractive appearance, the display panel requires narrower and narrower frames, so that the requirements on the thinning coating of the sealant and the performance of products are higher and higher, such as liquid crystal puncture resistance, under the requirement of thinning, the general sealant is difficult to meet the requirement of 0.5mm line width puncture, especially under the condition that the waiting time of some products is too long (more than 4 min) in the production process, the puncture of the general sealant is larger than 0.2mm and is far larger than the requirement of the products (less than 0.1 mm). Therefore, development of an adhesive with a line width of less than 0.5mm of a coating line is needed, and the requirement of less than 0.1mm of penetration of the adhesive line by liquid crystal can be met.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an adhesive composition, a preparation method and application thereof, wherein the adhesive can be used for preparing a display panel, and can meet the requirement that the penetration of liquid crystal to an adhesive line is less than 0.1mm under the condition that the line width of a coating line is less than 0.5 mm.
The technical scheme for solving the technical problems is as follows: an adhesive composition, the adhesive composition comprising: at least one resin contains epoxy functional groups which can be cured by heating, at least one resin contains acrylate groups which can be cured by UV light, at least one photoinitiator, at least one thermosetting agent which can react with the epoxy functional groups, a coupling agent and a modified filler;
and (3) placing the filler in A-187 or KH550 for ultrasonic treatment and heating treatment, and drying to obtain the modified filler.
Further, the adhesive composition comprises the following components in parts by weight: 5-70 parts of resin containing epoxy functional groups capable of being cured by heating, 10-60 parts of resin containing acrylate groups capable of being cured by UV light, 0.1-1 part of photoinitiator, 1-30 parts of thermosetting agent capable of reacting with the epoxy functional groups, 0.5-1.5 parts of coupling agent and 5-30 parts of modified filler.
In the composition of the adhesive composition, the dosage of the resin containing the epoxy functional groups capable of being cured by heating is less than 5 parts, so that the adhesive has poor adhesive force and cannot play a role in bonding, and if the dosage exceeds 70 parts, the brittleness of the adhesive after curing is increased, and the adhesive is easy to fall off to test cracking failure; the use amount of the resin containing the acrylate group capable of being cured by UV light is below 10 parts, the light curing component is too low, the pollution to liquid crystal is easy to cause, and the use amount exceeds 40 parts, so that the water resistance of the adhesive product is reduced, and the adhesive product is easy to lose effectiveness in high-temperature high-humidity test.
Preferably, the adhesive composition comprises the following components in parts by weight: 20-50 parts of resin containing epoxy functional groups capable of being cured by heating, 20-40 parts of resin containing acrylate groups capable of being cured by UV light, 0.1-1 part of photoinitiator, 1-20 parts of thermosetting agent capable of reacting with the epoxy functional groups, 0.5-1.5 parts of coupling agent and 10-20 parts of modified filler.
Further, the resin containing the epoxy functional group capable of being cured by heating is liquid resin or solid epoxy resin with the particle size below 3 um; the resin containing the epoxy functional group capable of being cured by heating is selected from any one or a combination of a plurality of aromatic epoxy resin, aliphatic epoxy resin or alicyclic epoxy resin.
The resin containing the heat-curable epoxy functional group preferably contains at least one epoxy group, and the number of epoxy groups contained in one molecule of the resin containing the heat-curable epoxy functional group is preferably 2 or more, and the larger the number of epoxy groups, the better the adhesion to the glass substrate.
Further, the resin containing the acrylate group capable of being cured by UV light is any one or a combination of a plurality of urethane acrylate and epoxy acrylate.
The resin molecule containing the UV-curable acrylate group contains 1 or more (meth) acrylate groups, and may be UV-curable, prepolymer or polymer, and preferably contains 2 or more (meth) acrylate groups.
Further, the photoinitiator is any one or a combination of a plurality of cracking free radical initiators or hydrogen abstraction free radical initiators.
Preferably, the photoinitiator preferably absorbs more than 350 nm.
Further, the thermosetting agent is any one or a combination of a plurality of hydrazide, imidazole or modified amine thermosetting agents.
As a component for curing the epoxy resin, an amine or anhydride curing agent is generally selected, and a curing agent with a latent function is selected, so that the viscosity of the adhesive product is stable in use.
Further, the filler is any one or a combination of a plurality of calcium carbonate, alumina, magnesium carbonate, silicon micropowder, silicon dioxide, glass microsphere, ABS or MBS, and the particle size of the filler is below 2 um.
The filler has the main functions of reducing the expansion coefficient and reducing the thermal stress in the adhesive and is divided into an inorganic filler and an organic filler, wherein the particle size of the filler is less than 2um, which is more beneficial to the stability of coating; more preferably, the filler is of a wide-distribution particle size, and the single-distribution filler is easy to cause integral sliding of the wet glue during bonding, and the wide-distribution particle size is beneficial to improving the adhesive force of the wet glue to the glass substrate and resisting penetration of liquid crystal.
Further, the resin containing the epoxy functional group which can be cured by heating is liquid resin which is selected from any one or a combination of a plurality of YD-128, GY 281, GY 282, GY 776, EPICLON 830-s, HP-4032 or HP-4032D;
the resin containing the acrylate group which can be cured by UV light is any one or a combination of more than one of DR-U028FS, DR-U065B, 6219-100, 623-100 or 623A-80;
the photoinitiator is any one or a combination of a plurality of Omnirad TPO, omnirad 184, omnirad 819, omnirad 1173 and Omnirad 907;
the thermosetting agent is any one or a combination of a plurality of VDH, UDH, PN-23J, FXR-1030, FXR-1081 or FXR-1121;
the coupling agent is KH560;
the filler is silica with the particle size ranging from 0.1 to 0.8um, namely, the silica with the particle sizes of 0.1um, 0.5um and 0.8um can be used as the filler by mixing, and the proportion of each particle size is not particularly limited.
Further, the first method for preparing the modified filler is as follows: dispersing filler in toluene, ultrasonically dispersing to obtain uniform suspension, adding A-187 into the suspension, heating to 85-95 ℃ under ultrasonic conditions for reacting for 9-11h, ultrasonically centrifuging, and drying to obtain modified filler; the mass ratio of A-187 to the filler is 1: (9-11);
the second method for preparing the modified filler is as follows: dissolving KH550 in deionized water, and regulating pH to 2-4 with glacial acetic acid to obtain KH550 solution; adding filler into ethanol water solution, performing ultrasonic dispersion to obtain mixed solution, adding KH550 solution into the mixed solution, heating to 85-95 ℃ under ultrasonic condition to react for 9-11h, performing ultrasonic centrifugation, and drying to obtain modified filler; the mass ratio of KH550 to filler is 1: (9-11).
The invention also discloses a preparation method of the adhesive composition, which comprises the following steps: and under a yellow light environment, sequentially weighing and adding the resin containing the epoxy functional groups capable of being cured by heating and the resin containing the acrylate groups capable of being cured by UV light into a double-planetary stirring kettle, adding a photoinitiator, heating and stirring to enable the photoinitiator to be completely fused into the resin, then adding a modified filler, stirring to enable materials to be uniform, then adding a coupling agent, finally adding a thermosetting agent, controlling the temperature of the materials to be below 30 ℃, stirring to enable all the materials to be uniform without obvious particles, and then grinding and dispersing the materials uniformly to obtain the adhesive composition.
The invention also discloses application of the adhesive composition, and the adhesive composition is applied to preparation of a liquid crystal display panel.
The beneficial effects of the invention are as follows:
according to the adhesive composition, the surface of the filler is modified, so that the liquid crystal puncture influence can be effectively improved, the adhesive composition can meet the requirement that the liquid crystal is less than 0.1mm for the puncture of the glue line under the line width of the coating line of less than 0.5mm, and the adhesive composition has higher adhesive strength.
The adhesive composition is applied to the field of display panels of double curing processes, can greatly reduce the puncture problem, has better stability and durability, and can avoid the problem of uneven images of the display panel, thereby showing stable and excellent display effect.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
An adhesive composition, the adhesive composition comprising: at least one resin contains epoxy functional groups which can be cured by heating, at least one resin contains acrylate groups which can be cured by UV light, at least one photoinitiator, at least one thermosetting agent which can react with the epoxy functional groups, a coupling agent and a modified filler;
and (3) placing the filler in A-187 or KH550 for ultrasonic treatment and heating treatment, and drying to obtain the modified filler.
Specifically, the adhesive composition comprises the following components in parts by weight: 5-70 parts of resin containing epoxy functional groups capable of being cured by heating, 10-60 parts of resin containing acrylate groups capable of being cured by UV light, 0.1-1 part of photoinitiator, 1-30 parts of thermosetting agent capable of reacting with the epoxy functional groups, 0.5-1.5 parts of coupling agent and 5-30 parts of modified filler.
Specifically, the resin containing the epoxy functional group capable of being cured by heating is liquid resin or solid epoxy resin with the particle size below 3 um; the resin containing the epoxy functional group capable of being cured by heating is selected from any one or a combination of a plurality of aromatic epoxy resin, aliphatic epoxy resin or alicyclic epoxy resin. The resin containing the heat-curable epoxy functional group may be synthesized by a known method or may be selected from commercially available ones.
Specifically, the resin containing an acrylate group which can be cured by UV light is any one or a combination of a plurality of urethane acrylate or epoxy acrylate.
Specifically, the photoinitiator is any one or a combination of a plurality of cracking free radical initiators or hydrogen abstraction free radical initiators; the thermosetting agent is any one or a combination of more than one of hydrazide, imidazole or modified amine thermosetting agents.
Specifically, the filler is any one or a combination of a plurality of calcium carbonate, alumina, magnesium carbonate, silicon micropowder, silicon dioxide, glass microsphere, ABS or MBS, and the particle size of the filler is below 2 um.
Specifically, the resin containing an epoxy functional group which can be cured by heating (in the embodiment, simply referred to as epoxy resin) is a liquid resin and is selected from any one or a combination of a plurality of commercially available YD-128, GY 281, GY 282, GY 776, EPICLON 830-s, HP-4032 or HP-4032D;
the resin containing acrylate groups which can be cured by UV light (the acrylic acid ester is abbreviated as acrylic acid ester in the embodiment) is any one or a combination of a plurality of DR-U028FS, DR-U065B, 6219-100, 623-100 or 623A-80 which are sold in the market;
the photoinitiator is any one or a combination of a plurality of commercial Omnirad TPO, omnirad 184, omnirad 819, omnirad 1173 and Omnirad 907;
the thermosetting agent is any one or a combination of a plurality of commercial VDH, UDH, PN-23J, FXR-1030, FXR-1081 or FXR-1121;
the coupling agent is KH560 (silane coupling agent);
the filler is silicon dioxide with the particle size ranging from 0.1 to 0.8 um.
Specifically, the first method for preparing the modified filler comprises the following steps: dispersing filler in toluene, ultrasonically dispersing to obtain uniform suspension, adding A-187 into the suspension, heating to 85-95 ℃ under ultrasonic conditions for reacting for 9-11h, ultrasonically centrifuging, and drying to obtain modified filler; the mass ratio of A-187 to the filler is 1: (9-11);
the second method for preparing the modified filler is as follows: dissolving KH550 in deionized water, and regulating pH to 2-4 with glacial acetic acid to obtain KH550 solution; adding filler into ethanol water solution, performing ultrasonic dispersion to obtain mixed solution, adding KH550 solution into the mixed solution, heating to 85-95 ℃ under ultrasonic condition to react for 9-11h, performing ultrasonic centrifugation, and drying to obtain modified filler; the mass ratio of KH550 to filler is 1: (9-11).
The preparation method of the adhesive composition comprises the following steps: and under a yellow light environment, sequentially weighing and adding the resin containing the epoxy functional groups capable of being cured by heating and the resin containing the acrylate groups capable of being cured by UV light into a double-planetary stirring kettle, adding a photoinitiator, heating and stirring to enable the photoinitiator to be completely fused into the resin, then adding a modified filler, stirring to enable materials to be uniform, then adding a coupling agent, finally adding a thermosetting agent, controlling the temperature of the materials to be below 30 ℃, stirring to enable all the materials to be uniform without obvious particles, and then grinding and dispersing the materials uniformly to obtain the adhesive composition.
The adhesive composition is applied to the preparation of liquid crystal display panels. The specific method comprises the following steps: first, a square frame is coated with an adhesive composition on one glass substrate, then a liquid crystal is dropped into the frame, and finally the other glass substrate is vacuum bonded, and a UV lamp is used for 3000mj/m 2 And (3) pre-curing, and finally, final curing at 120 ℃/60 min.
1. Preparation examples of modified fillers
Example 1-1
Preparation of modified filler A-1:
dispersing 10 parts of silicon dioxide (with the particle size ranging from 0.1 to 0.8 um) in 1000 parts of toluene, performing ultrasonic dispersion for 60min to obtain a uniform suspension, adding 1 part of A-187 into the suspension, performing ultrasonic treatment for 20min, performing reaction in a constant-temperature water bath at 90 ℃ for 10h, performing ultrasonic centrifugation for 10 times, and performing vacuum drying to obtain the modified filler A-1.
Examples 1 to 2
Preparation of modified filler A-2:
1 part of KH550 is weighed and dissolved in 50 parts of deionized water, and the pH is adjusted to 3 by glacial acetic acid to obtain KH550 solution; adding 10 parts of silicon dioxide (with the particle size range of 0.1-0.8 um) into 2000 parts of ethanol water solution (the volume ratio of ethanol to water is 1:1), and performing ultrasonic dispersion for 60min to obtain a mixed solution; adding KH550 solution into the mixed solution, then carrying out ultrasonic treatment for 20min, reacting for 10h in a constant-temperature water bath at 90 ℃, carrying out ultrasonic centrifugation for 10 times, and carrying out vacuum drying to obtain the modified filler A-2.
Examples 1 to 3
Preparation of modified filler A-3:
dispersing 9 parts of silica micropowder (with the particle size range of less than 2 um) in 1000 parts of toluene, performing ultrasonic dispersion for 60min to obtain uniform suspension, adding 1 part of A-187 into the suspension, performing ultrasonic reaction for 9h in a constant-temperature water bath at the temperature of 90 ℃ for 20min, performing ultrasonic centrifugation for 10 times, and performing vacuum drying to obtain the modified filler A-3.
Examples 1 to 4
Preparation of modified filler A-4:
dispersing 11 parts of calcium carbonate (with the particle size range smaller than 2 um) in 1000 parts of toluene, performing ultrasonic dispersion for 60min to obtain a uniform suspension, adding 1 part of A-187 into the suspension, performing ultrasonic treatment for 25min, performing reaction for 9h in a constant-temperature water bath at 90 ℃, performing ultrasonic centrifugation for 10 times, and performing vacuum drying to obtain the modified filler A-4.
2. Adhesive composition examples
The specific process method comprises the following steps: all the operations are carried out under a yellow light environment, epoxy resin and acrylic resin are weighed in sequence and added into a double-planetary stirring kettle, the temperature is increased to 40 ℃, stirring is carried out, the photoinitiator is completely fused into the epoxy resin and the acrylic resin, then modified filler is added, after stirring, materials are uniform, then coupling agent KH560 is added, finally a thermosetting agent is added, the temperature of the materials is controlled below 30 ℃, stirring is carried out, all the materials are uniform and have no obvious particles, and then the materials are ground and dispersed, so that solid powder and liquid materials are further mixed and dispersed uniformly, and the adhesive composition is obtained.
Examples 2-1 to 2-6 were carried out according to the above process except that the corresponding raw materials and proportions were changed.
Comparative example 1
An adhesive composition was prepared in the same manner as in example 2-1, except that an unmodified filler was used in the formulation of the adhesive composition, specifically silica (particle size range 0.1 to 0.8 um) before A-1 was used as the filler.
Comparative example 1
Adhesive compositions were prepared in the same manner as in examples 2-4, except that unmodified filler was used in the formulation of the adhesive composition, and specifically, silica fume (particle size less than 2 um) before A-3 was used as filler.
Specific raw materials and amounts thereof in examples 2-1 to 2-6 and comparative examples 1-2 are shown in Table 1 below.
Table 1 raw materials data table for adhesive composition examples
3. Performance testing of adhesive compositions
The adhesive combinations prepared in examples 2-1 to 2-6 and comparative examples 1 and 2 were subjected to performance test in the following manner.
(1) Puncture depth test: coating the adhesive composition in the shape of a Chinese character kou on a glass substrate by using a dispenser, dripping liquid crystal in a frame, vacuum bonding the other glass substrate, waiting for 4min, entering a UV light curing box, and irradiating 3000mj/cm 2 Energy, then enter into a blast drying box to heat for 120 DEG/60 min, and observe the depth of liquid crystal entering into a glue line under a microscope.
(2) Adhesion test: according to the scheme in the puncture depth test, 3cm of glass is coated, liquid crystal is not dripped, then another piece of glass is attached in vacuum, the same photo-curing and thermal curing processes are carried out, and after waiting for 24 hours at normal temperature, the adhesive force is tested on a universal tensile machine.
(3) Coating line width test: the adhesive composition was directly applied to glass with a dispenser and the line width was checked under a microscope after vacuum lamination.
Specific performance test data are shown in table 3 below:
table 3 performance test data
| Penetration depth [ um ]] | Adhesive strength [ N/mm ]] | Coating line width [ mm ]] | |
| Example 2-1 | 90 | 9.5 | 0.5 |
| Example 2-2 | 30 | 12 | 0.5 |
| Examples 2 to 3 | 75 | 10 | 0.5 |
| Examples 2 to 4 | 80 | 9.5 | 0.5 |
| Examples 2 to 5 | 45 | 11 | 0.5 |
| Examples 2 to 6 | 50 | 11 | 0.5 |
| Comparative example 1 | 300 | 10 | 0.5 |
| Comparative example 2 | 320 | 8.5 | 0.5 |
The experimental data show that the technical scheme of the adhesive composition is more beneficial to enabling the adhesive composition to meet the requirement of liquid crystal on smaller penetration of adhesive lines under the condition of smaller line width of coating lines, and the adhesive composition has higher adhesive strength.
The adhesive composition is applied to the field of display panels of double curing processes, can greatly reduce the puncture problem, has better stability and durability, and can avoid the problem of uneven images of the display panel, thereby showing stable and excellent display effect.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (10)
1. An adhesive composition, characterized in that the adhesive composition comprises: at least one resin contains epoxy functional groups which can be cured by heating, at least one resin contains acrylate groups which can be cured by UV light, at least one photoinitiator, at least one thermosetting agent which can react with the epoxy functional groups, a coupling agent and a modified filler;
and (3) placing the filler in A-187 or KH550 for ultrasonic treatment and heating treatment, and drying to obtain the modified filler.
2. The adhesive composition according to claim 1, wherein the adhesive composition comprises, in parts by weight: 5-70 parts of resin containing epoxy functional groups capable of being cured by heating, 10-60 parts of resin containing acrylate groups capable of being cured by UV light, 0.1-1 part of photoinitiator, 1-30 parts of thermosetting agent capable of reacting with the epoxy functional groups, 0.5-1.5 parts of coupling agent and 5-30 parts of modified filler.
3. An adhesive composition according to claim 1, wherein the resin containing heat-curable epoxy functional groups is a liquid resin or a solid epoxy resin having a particle size of 3 μm or less; the resin containing the epoxy functional group capable of being cured by heating is selected from any one or a combination of a plurality of aromatic epoxy resin, aliphatic epoxy resin or alicyclic epoxy resin.
4. An adhesive composition according to claim 1, wherein the resin containing UV light curable acrylate groups is any one or a combination of urethane acrylate or epoxy acrylate.
5. The adhesive composition according to claim 1, wherein the photoinitiator is any one or a combination of a cleavage type radical initiator or a hydrogen abstraction type radical initiator;
the thermosetting agent is any one or a combination of more than one of hydrazide, imidazole or modified amine thermosetting agents.
6. The adhesive composition of claim 1, wherein the filler is any one or a combination of calcium carbonate, aluminum oxide, magnesium carbonate, silica micropowder, silica, glass microsphere, ABS or MBS, and the particle size of the filler is 2um or less.
7. The adhesive composition of claim 1, wherein the resin containing heat curable epoxy functional groups is a liquid resin selected from any one or more of YD-128, GY 281, GY 282, GY 776, EPICLON 830-s, HP-4032, and HP-4032D;
the resin containing the acrylate group which can be cured by UV light is any one or a combination of more than one of DR-U028FS, DR-U065B, 6219-100, 623-100 or 623A-80;
the photoinitiator is any one or a combination of a plurality of Omnirad TPO, omnirad 184, omnirad 819, omnirad 1173 and Omnirad 907;
the thermosetting agent is any one or a combination of a plurality of VDH, UDH, PN-23J, FXR-1030, FXR-1081 or FXR-1121;
the coupling agent is KH560;
the filler is silicon dioxide with the particle size ranging from 0.1 to 0.8 um.
8. An adhesive composition according to claim 7, wherein the modified filler is prepared by a process comprising: dispersing filler in toluene, ultrasonically dispersing to obtain uniform suspension, adding A-187 into the suspension, heating to 85-95 ℃ under ultrasonic conditions for reacting for 9-11h, ultrasonically centrifuging, and drying to obtain modified filler; the mass ratio of A-187 to the filler is 1: (9-11);
the second method for preparing the modified filler is as follows: dissolving KH550 in deionized water, and regulating pH to 2-4 with glacial acetic acid to obtain KH550 solution; adding filler into ethanol water solution, performing ultrasonic dispersion to obtain mixed solution, adding KH550 solution into the mixed solution, heating to 85-95 ℃ under ultrasonic condition to react for 9-11h, performing ultrasonic centrifugation, and drying to obtain modified filler; the mass ratio of KH550 to filler is 1: (9-11).
9. A method for preparing an adhesive composition according to any one of claims 1-8, characterized in that under a yellow light environment, a resin containing an epoxy functional group which can be cured by heating and a resin containing an acrylate group which can be cured by UV light are sequentially weighed and added into a double-planetary stirring kettle, a photoinitiator is added, heating and stirring are performed to enable the photoinitiator to be completely integrated into the resin, then a modified filler is added, after stirring, materials are made uniform, then a coupling agent is added, finally a thermosetting agent is added, the temperature of the materials is controlled below 30 ℃, stirring is performed to enable all the materials to be uniform, no obvious particles are generated, and then grinding and dispersing are performed on the materials uniformly to obtain the adhesive composition.
10. Use of an adhesive composition according to any one of claims 1-8 or an adhesive composition prepared by the method of preparation according to claim 9, wherein the adhesive composition is used for the preparation of liquid crystal display panels.
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