CN115449326B - Impact-resistant UV (ultraviolet) curing cofferdam adhesive and preparation method thereof - Google Patents
Impact-resistant UV (ultraviolet) curing cofferdam adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN115449326B CN115449326B CN202211242271.9A CN202211242271A CN115449326B CN 115449326 B CN115449326 B CN 115449326B CN 202211242271 A CN202211242271 A CN 202211242271A CN 115449326 B CN115449326 B CN 115449326B
- Authority
- CN
- China
- Prior art keywords
- diisocyanate
- cofferdam
- oligomer
- polyurethane
- impact
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3812—Polyhydroxy compounds having fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6423—Polyalkylene polyamines; polyethylenimines; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6535—Compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/6755—Unsaturated carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides an impact-resistant UV curing cofferdam adhesive and a preparation method thereof, and the impact-resistant UV curing cofferdam adhesive comprises the following raw materials: the polyurethane acrylate polyurethane comprises polyester acrylate oligomer, branched polyurethane acrylate oligomer, filler and auxiliary agent, wherein the branched polyurethane acrylate oligomer is prepared by reacting fluorine-containing dihydric alcohol with diisocyanate to prepare isocyanate-terminated polyurethane oligomer, then reacting the isocyanate-terminated polyurethane oligomer with diethanolamine and dendritic polymer to obtain dendritic polyurethane oligomer, and finally, the dendritic polyurethane oligomer is blocked by an acryloyl chloride compound, wherein the diisocyanate is compounded by aromatic diisocyanate and aliphatic diisocyanate. The invention can ensure that the cofferdam adhesive has good impact resistance and low thermal linear expansion coefficient under the condition of small glass transition temperature drop by adjusting the composition of diisocyanate which is a preparation raw material of branched polyurethane acrylic ester oligomer and the relative dosage of two main resins.
Description
Technical Field
The invention belongs to the technical field of UV curing adhesives, and particularly relates to an impact-resistant UV curing cofferdam adhesive and a preparation method thereof.
Background
In the electronic industry, thermal stress and mechanical stress are the main causes of failure of the integrated circuit structure, and most of failure occurs at the joint of the chip and the circuit board, and the joint is composed of a large number of micro-sized welding spots, so that the deformation adaptability of the joint is very small, the joint is extremely sensitive to the thermal stress and the mechanical stress, and the reliability problem of the integrated circuit is more remarkable.
The underfill is a technology for improving the stability and reliability of the electronic product in a severe environment, can effectively slow down impact load and thermal load, can improve the performances of deformation resistance, chemical corrosion resistance and the like of the packaged chip, and can greatly improve the fatigue life of the packaged chip, so that the underfill has great development potential. The bottom filling mode comprises two modes of bottom full filling and four-corner peripheral filling, wherein the glue used for the bottom full filling is called bottom filling glue, and the glue used for the four-corner peripheral filling is called cofferdam glue, dam surrounding glue or four-corner binding glue. Because the use positions of the two types of glue are different, the performances of the two types of glue are greatly different: the underfill requires good fluidity of the glue so that the bottom of the chip is quickly filled with the glue by utilizing the capillary effect of the liquid; the cofferdam glue needs to have good thixotropic property, so that the glue is not easy to flow, and the glue moves very little after dispensing, thereby avoiding the elements which do not need to be filled from being filled or influencing the buckle shielding cover. The bottom filling process is obviously affected by 'edge effect', the bottom filling degree is low, the protection function to welding spots is weakened, the cofferdam glue forms an important research and development object of current scientific research personnel, such as patent CN201410795290.3 and CN201710294375.7, LOCTITE3128 and LOCTITE3128NH of the Lotai company, and 9422-SC and 9309-SC of the DYMAX company are all cofferdam glue, wherein 9422-SC and 9309-SC of the DYMAX company are two novel UV curing acrylic polyurethane cofferdam glue, compared with the traditional organic silicon type and epoxy cofferdam glue, the curing rate is high, the curing can be completed within several seconds to twenty seconds, and the cofferdam glue is suitable for industrial continuous automatic production of integrated circuits, but the two UV curing acrylic polyurethane cofferdam glue has the advantages of low crosslinking degree and low glass transition temperature of between 60 ℃ and 70 ℃, and the risk of falling, impact, extrusion and vibration and protection are faced with the risk of rupture protection when the temperature of the integrated circuit is higher than Tg, so the two cofferdam glue is more suitable for being applied to electronic books, desktop computers, electronic books, electronic computers, outdoor communication equipment, electronic base station equipment, and the like, and the electronic base station is suitable for severe environment, and the environment of the electronic communication equipment.
In summary, developing an impact-resistant UV-cured dam adhesive with both a low coefficient of thermal expansion and a high glass transition temperature is of great importance in expanding the application of dam adhesives in portable electronic devices and electronic devices operating in harsh environments.
Disclosure of Invention
In order to solve the problems, the invention provides an impact-resistant UV-cured cofferdam adhesive and a preparation method thereof, wherein main resin of the cofferdam adhesive comprises polyester acrylate oligomer and branched polyurethane acrylate oligomer, and the composition of raw material diisocyanate prepared from the branched polyurethane acrylate oligomer and the relative dosage of the two main resins are adjusted, so that the cofferdam adhesive has good impact resistance and low thermal linear expansion coefficient under the condition of small glass transition temperature drop.
In order to achieve the above purpose, the following specific technical scheme is adopted:
an impact-resistant UV curing cofferdam adhesive comprises the following raw materials: the polyurethane acrylate polyurethane comprises polyester acrylate oligomer, branched polyurethane acrylate oligomer, reactive diluent, filler, coupling agent, thixotropic agent, photoinitiator and polymerization inhibitor, wherein the branched polyurethane acrylate oligomer is prepared by reacting fluorine-containing dihydric alcohol with diisocyanate firstly, then the isocyanate-terminated polyurethane oligomer reacts with diethanolamine and dendritic polymer to obtain dendritic polyurethane oligomer, finally the dendritic polyurethane oligomer is blocked by an acryloyl chloride compound, and the diisocyanate is prepared by compounding aromatic diisocyanate and aliphatic diisocyanate.
Further, the impact-resistant UV curing cofferdam adhesive comprises the following raw materials in parts by weight: 20-25 parts of polyester acrylate oligomer, 10-15 parts of branched polyurethane acrylate oligomer, 5-10 parts of reactive diluent, 40-70 parts of filler, 0.3-1 part of coupling agent, 2.5-4.5 parts of thixotropic agent, 0.1-3 parts of photoinitiator and 0.01-0.03 part of polymerization inhibitor, wherein the molar ratio of diisocyanate, fluorine-containing dihydric alcohol, diethanolamine, dendritic polymer and acrylic chloride compound is 2.11-2.16:1:0.92-0.95:0.22-0.24:1.84-1.9; the molar ratio of the aromatic diisocyanate to the aliphatic diisocyanate is 1:7-9.
The aliphatic diisocyanate is selected from one or a combination of two or more of 1, 6-hexamethylene diisocyanate, decane-1, 10-diisocyanate, trimethyl hexamethylene diisocyanate, trimethyl-1, 6-diisocyanatohexane, methylene diisocyanate and lysine ester diisocyanate.
Preferably, the aliphatic diisocyanate is selected from one or a combination of two or more of 1, 6-hexamethylene diisocyanate, decane-1, 10-diisocyanate and trimethylhexamethylene diisocyanate.
The aromatic diisocyanate is selected from one or a combination of two or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -methylene bis (phenyl isocyanate), m-xylylene diisocyanate and p-xylylene diisocyanate. Preferably, the aromatic diisocyanate is selected from one or a combination of two of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
The main chain carbon number of the fluorine-containing dihydric alcohol is 4-10, specifically selected from octafluoro-1, 6-hexanediol, 2,3, 4-hexafluoro-1, 5-pentanediol 1H, 10H-perfluoro-1, 10-decanediol, 1H, 8H-dodecafluoro-1, 8-octanediol one or two or more of 1H, 9H-perfluoro-1, 9-nonanediol, tetrafluorobutanediol, 2,3, 4-hexafluoro-cyclo-1, 5-pentanediol and 3,3,4,4,5,5,6,6-octafluoro-octane-1, 8-diol.
Preferably, the main chain carbon number of the fluorine-containing dihydric alcohol is 8-10, selected from 1H, 10H-perfluoro-1, 10-decanediol, 1H, 8H-dodecafluoro-1, 8-octanediol one or two or more of 1H, 9H-perfluoro-1, 9-nonanediol and 3,3,4,4,5,5,6,6-octafluorooctane-1, 8-diol.
The dendritic polymer is a polypropylene imine dendritic polymer, and the algebra is 1.0 generation; the polypropylene imine dendrimer comprises one or a combination of two or more of polypropylene imine triamine dendrimer, polypropylene imine diamine dendrimer and polypropylene imine tetramine dendrimer.
The acrylic chloride compound is selected from one or a combination of two or more of acrylic chloride, methacrylic chloride and 2-ethyl acrylic chloride, preferably methacrylic chloride.
The branched urethane acrylate oligomer is prepared by a process comprising the steps of:
4) Adding diisocyanate and an organic solvent into a reaction kettle under an inert atmosphere, stirring until the diisocyanate and the organic solvent are uniform, heating and keeping the temperature constant, dropwise adding a fluorine-containing dihydric alcohol solution under the stirring condition for reaction, cooling to room temperature after the reaction is finished, and performing column chromatography to obtain an isocyanate-terminated polyurethane oligomer;
5) Under inert atmosphere, dissolving the isocyanate-terminated polyurethane oligomer obtained in the step 1) in an organic solvent, cooling and keeping the temperature, dropwise adding a diethanolamine solution, and carrying out one-step reaction at the constant temperature under the stirring condition; dripping dendritic polymer solution after the reaction is finished, performing two-step reaction at constant temperature, naturally recovering to room temperature after the reaction is finished, and performing column chromatography to obtain dendritic polyurethane oligomer;
6) Under inert atmosphere, dissolving the dendritic polyurethane oligomer obtained in the step 2), an acid binding agent and a stabilizer in an organic solvent, dropwise adding an acryloyl chloride compound solution under the ice water bath condition, reacting at constant temperature, dropwise adding an alkali solution to be neutral after the reaction is finished, and distilling under reduced pressure to obtain the branched polyurethane acrylate oligomer.
The organic solvent in the step 1) is selected from one or a combination of two or more of DMF, DMSO, acetonitrile, acetone, diethyl ether, benzene and xylene; the temperature is raised to 40-80 ℃, and the concentration of the fluorine-containing dihydric alcohol solution is 10-30wt%; the stirring speed is 300-500r/min, the dripping speed of the fluorine-containing dihydric alcohol solution is 0.5-1 drop/second, the reaction time is 1-5h, the column chromatography eluent is benzene/acetone, and the volume ratio is 1-3:1.
The temperature of the step 2) is reduced to (-5 ℃) to minus 5 ℃; the organic solvent is the same as the organic solvent in the step 1); the concentration of the diethanolamine solution is 10-30wt% and the dripping time is 10-30min; the constant temperature one-step reaction time is 1-3h; the concentration of the dendritic polymer solution is 10-30wt%, the dripping time is 20-60min, the constant temperature two-step reaction time is 1-3h, and the eluent for column chromatography is benzene/ethyl acetate 1-3:1. And 2) controlling the temperature at a low temperature section by utilizing different reactivity of hydroxyl, amino and isocyanate to enable the amino to react with the isocyanate, and enabling the hydroxyl to not react with the isocyanate to prepare the dendritic polyurethane oligomer.
The catalyst in the step 3) is selected from one or more of triethylamine, triethylenediamine and N, N-dimethylcyclohexylamine, the molar ratio of the acid binding agent to the acrylic chloride compound is 1:1.84-1.9, the stabilizer is selected from one or more of hydroquinone, p-methoxyphenol and 2, 6-di-tert-butyl-p-cresol, the stabilizer is used in an amount of 0.1-0.5wt% of the acrylic chloride compound, the concentration of the acrylic chloride compound solution is 5-10wt% and the reaction time is 20-60min, the constant temperature reaction time is 1-3h, the organic solvent is the same as the organic solvent in the step 1), and alkali liquor is not particularly limited, and the stabilizer is one or two of saturated sodium hydroxide solution and sodium bicarbonate solution commonly used in the field.
The polyester acrylic acid ester oligomer is prepared by acrylic acid ester of low molecular weight polyester diol, the functionality of the polyester acrylic acid ester oligomer is 2-6, and the viscosity is 2000-20000cP (25 ℃).
The polyester acrylate oligomer is selected from one or a combination of two or more of Photomer 5430, cyanogen EB450, cyanogen EB657, cyanogen EB800, DMI PEAM-645, DMI PEAM-1044, DMI PEM-665, DMI PEAM-1769 and DMI PEM-1066.
Preferably, the polyester acrylate oligomer has a functionality of 2-3 and a viscosity of 2000-10000cP (25 ℃) and is selected from one or a combination of two or more of DMI PEAM-645, DMI PEAM-1044 and DMI PEM-665.
More preferably, the polyester acrylate oligomer is DMI PEAM-645.
The polyester acrylic acid ester oligomer DMI PEAM-645 is a medium-low viscosity oligomer, the molecular main chain of the polyester acrylic acid ester oligomer comprises a structural unit formed by tricyclo [5.2.1.0,2,6] decanedimethanol and isophthalic acid, and the oligomer molecule is rigid, so that the cofferdam glue formed by the polyester acrylic acid ester oligomer has higher glass transition temperature and lower low thermal linear expansion coefficient.
The reactive diluent is not particularly limited, and is usually used in the art, and is selected from one or a combination of two or more of isobornyl acrylate, cyclohexyl methacrylate, dicyclopentadiene methacrylate, isobornyl methacrylate, methacrylic acid, and dicyclopentadiene acrylate.
The filler is silica micropowder with refractive index of 1.45-1.6 and particle diameter of 0.5-10 μm.
The silicon micropowder is selected from one or more of SF102, SF106, SF202, SF210, SF400, SF600, or Japanese elegance Dou Ma SC2500SMJ, SC5500 SMJ.
The coupling agent is selected from one or a combination of two or more of vinyl trimethoxy silane, vinyl triethoxy silane, gamma-methacryloxypropyl trimethoxy silane and gamma-glycidoxypropyl trimethoxy silane.
The thixotropic agent comprises one or a combination of two or more of fumed silica, organic bentonite, hydrogenated castor oil and polyamide wax.
The thixotropic agent is preferably fumed silica, the average particle size of primary particles of the fumed silica is 5-50nm, and the specific surface area is 100-300m 2 /g。
The fumed silica is selected from one or a combination of more than two of winning wound R202, R974, wake H18, H15, kabott TS620, TS 720.
The initiator is a cleavage type free radical photoinitiator, is selected from one or a combination of two or more of benzoin initiator, alpha-hydroxy ketone initiator, alpha-amino ketone initiator and acyl phosphine oxide initiator, and can be selected from one or a combination of two or more of Darocur1173, irgacure184, irgacure651, irgacure819, irgacure907 and Irgacure TPO of Pasteur.
The polymerization inhibitor is selected from one or a combination of two or more of hydroquinone, p-methoxyphenol and 2, 6-di-tert-butyl p-cresol.
The UV curing cofferdam adhesive can also comprise 0.05-0.2 part of dispersing agent and 0.1-0.5 part of defoaming agent.
The dispersing agent is selected from one or a combination of two or more of BYK110, BYK163, BYK9010 and BYK 9076.
The defoamer is selected from one or a combination of two or more of BYK 088 and BYK 080A, TEGO 3062.
The invention also provides a preparation method of the UV curing cofferdam adhesive, which comprises the following steps:
adding the polyester acrylate oligomer, the branched polyurethane acrylate oligomer, the reactive diluent, the coupling agent, the photoinitiator and the polymerization inhibitor into a mixer, mixing until uniform, adding the filler and the thixotropic agent, vacuumizing, continuously stirring until uniform, and packaging to obtain the UV curing cofferdam adhesive.
The application method of the UV curing cofferdam glue comprises the steps of passing the UV curing cofferdam glue through a glue dispenser, dispensing on the periphery of four corners of an electronic component, and then curing by ultraviolet irradiation.
The power of the ultraviolet light is 100-300mW/cm 2 The illumination time is 10-60s, and the illumination distance is 10-40cm.
The line width of the glue after the glue is dispensed by the glue dispenser is 0.5-5mm, and the height of the glue line is 0.5-3mm.
The dispensing path of the dispenser is selected from one of linear type and L-shaped.
Compared with the prior art, the invention has the beneficial effects that:
the main resin of the cofferdam glue comprises polyester acrylate oligomer and branched polyurethane acrylate oligomer, and the composition of diisocyanate which is a preparation raw material of the branched polyurethane acrylate oligomer and the relative dosage of the two main resins are adjusted, so that the cofferdam glue has good impact resistance and low thermal linear expansion coefficient under the condition that the glass transition temperature is not greatly reduced.
The preparation method is simple, green and environment-friendly, and is suitable for industrial production.
Drawings
FIG. 1 is a thermo-mechanical graph of an impact resistant UV dam adhesive prepared in application example 1;
fig. 2 is a photograph of the impact-resistant UV cofferdam glue prepared in application example 1 after dispensing and curing.
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited to the disclosure. Unless otherwise specified, "parts" are parts by weight in the examples of the present invention. All reagents used are those commercially available in the art.
The polypropylene imine diamine dendrimer was purchased from south kyphosis biotechnology limited company for 1.0 generation,
the polypropyleneimine triamine dendrimer was purchased from Nanjing Shizhou Biotechnology Co.Ltd.1.0 generation.
DMI PEAM-645 and DMI PEAM-665 are all available from Designer Molecules Inc.
Cyte EB800 is available from cyte corporation of the united states.
Preparation of branched polyurethane acrylate oligomers
Preparation example 1
1) Under nitrogen atmosphere, 0.216mol of diisocyanate formed by mixing 2, 4-toluene diisocyanate, 1, 6-hexamethylene diisocyanate according to a mole ratio of 1:7, 60g of DMF and 20g of acetone are added into a reaction kettle, stirring is carried out for 30min at a rotating speed of 300r/min, the temperature is raised to 70 ℃, 462.1g of 1H, 10H-perfluoro-1, 10-decanediol (solvent is DMF) with the concentration of 10wt% is dropwise added at the speed of 1 drop/second under the stirring condition, the constant temperature reaction is carried out for 3h after the dropwise addition, the reaction is carried out, the room temperature is naturally cooled after the reaction is finished, the isocyanate-terminated polyurethane oligomer is obtained by separating by a silica gel column, and the eluent is benzene/acetone and is obtained by mixing according to the volume ratio of 1.5:1.
2) Under nitrogen atmosphere, dissolving the isocyanate-terminated polyurethane oligomer obtained in the step 1) in a solvent consisting of 80g of DMF and 20g of acetone, cooling to 0 ℃, dropwise adding 96.8g of diethanolamine solution (the solvent is DMF) with the concentration of 10wt% and 20min of the solution, carrying out one-step reaction for 2 hours at the speed of 300r/min and keeping the constant temperature, dropwise adding 63.5g of solution (the solvent is DMF) with the concentration of 10wt% of the polypropylene imine diamine dendrimer 1.0 for 2 hours after the reaction, carrying out two-step reaction for 2 hours at the speed of 300r/min and keeping the constant temperature, naturally recovering to room temperature after the reaction is finished, separating the dendritic polyurethane oligomer by column chromatography, and mixing the eluent with benzene/ethyl acetate according to the volume ratio of 2:1.
3) Under the nitrogen atmosphere, dissolving 10.1g of triethylamine and 0.02g of 2, 6-di-tert-butyl-p-cresol in 100g of DMF and 10g of acetone, dropwise adding 385.9g of 5wt% concentration methacrylic chloride solution (solvent DMF) under the ice water bath condition, carrying out constant temperature reaction for 1h after 30min, dropwise adding saturated sodium bicarbonate solution to be neutral after the reaction is finished, and carrying out reduced pressure distillation to obtain the branched polyurethane acrylate oligomer.
Preparation example 2
The remainder was the same as in preparation example 1, except that the diisocyanate was mixed with 2, 4-toluene diisocyanate and 1, 6-hexamethylene diisocyanate in a molar ratio of 1:9.
Preparation example 3
The remainder was the same as in preparation example 1, except that the diisocyanate was mixed with 2, 4-toluene diisocyanate and 1, 6-hexamethylene diisocyanate in a molar ratio of 1:6.
Preparation example 4
The remainder was the same as in preparation example 1, except that the diisocyanate was mixed with 2, 4-toluene diisocyanate and 1, 6-hexamethylene diisocyanate in a molar ratio of 1:10.
Preparation example 5
The remainder was the same as in preparation example 1 except that trimethylhexamethylene diisocyanate was used in an equimolar amount in place of 1, 6-hexamethylene diisocyanate.
Preparation example 6
The remainder was the same as in preparation example 1 except that 2, 4-toluene diisocyanate was replaced with an equimolar amount of 4,4' -methylenebis (phenyl isocyanate).
Preparation example 7
The remainder was the same as in preparation example 1 except that 1H, 10H-perfluoro-1, 10-decanediol was replaced with an equimolar amount of octafluoro-1, 6-hexanediol solution.
Preparation example 8
The remainder was the same as in preparation example 1 except that 1, 6-hexamethylene diisocyanate was replaced with an equimolar amount of methylene diisocyanate.
Preparation example 9
The remainder was the same as in preparation example 1 except that the amount of diisocyanate obtained by mixing 2, 4-toluene diisocyanate and 1, 6-hexamethylene diisocyanate in a molar ratio of 1:9 was 0.211mol.
Comparative preparation example 1
The remainder was the same as in preparation example 1 except that the diisocyanate did not contain 1, 6-hexamethylene diisocyanate and that 0.216mol of diisocyanate was composed of all 2, 4-toluene diisocyanate.
Preparation of impact-resistant UV curing cofferdam adhesive
Example 1
25 parts of DMI PEAM-645, 15 parts of branched polyurethane acrylic ester oligomer prepared in preparation example 1, 3 parts of dicyclopentadiene acrylic ester, 3 parts of methacrylic acid, 1 part of gamma-glycidoxypropyl trimethoxysilane, 2 parts of Irgacure184, 0.2 part of Irgacure TPO, 0.8 part of Irgacure819 and 0.01 part of hydroquinone are added into a mixer to be mixed until uniform, 48.8 parts of SC5500SMJ and 4.5 parts of cabot TS720 are added, vacuumizing is continued, stirring is continued until uniform, and packaging is carried out, thus obtaining the UV curing cofferdam adhesive.
Examples 2 to 9
The remainder was the same as in example 1, except that the branched urethane acrylate oligomer used was prepared corresponding to preparation examples 2 to 9, respectively.
Example 10
The remainder was the same as in example 1 except that DMI PEAM-645 was used in an amount of 20 parts and the branched urethane acrylate oligomer prepared in preparation example 1 was used in an amount of 10 parts.
Comparative example 1
The remainder is the same as in example 1, except that the branched urethane acrylate oligomer used was prepared in comparative example 1.
Application example 1
The UV curing cofferdam glue prepared in the above example 1 was dispensed on four corners of a 15mm×20mm chip on a hard PCB circuit board by using an Shitong SEC-DP300 dispenser in an L-type dispensing path, the width of the glue line was 2.5mm, the height of the glue line was 2mm, and then the power was 100mW/cm 2 Is irradiated under an ultraviolet lamp for 60s, and the lamp distance is 20cm.
Application examples 2 to 10, comparative application example 1
The other was the same as in application example 1 except that UV-curable dam adhesives were used corresponding to those prepared in examples 2 to 10 and comparative example 1, respectively.
The following performance tests were carried out on the UV-curable dam adhesives prepared in the above application examples 1 to 10 and comparative application example 1:
before curing
Thixotropic coefficient: the viscosity of the same rotor at 5rpm and 50rpm respectively was tested by a rotary viscometer, and the ratio of the two was the thixotropic coefficient.
Viscosity: the test was carried out using a rotational viscometer at 25 ℃.
Curing speed: the ultraviolet curing machine is made by the Heteronetde photoelectric technology Co., ltd in Shenzhen city, model: htbx— light source: 365nm, power: 100mW/cm 2 When the hardness reaches 90D, the curing is judged to be complete, and the hardness is measured by referring to ASTM D2240.
After curing
Glass transition temperature: GB/T36800.2-2018 plastics thermo-mechanical analysis (TMA) part 2: measurement of the coefficient of linear thermal expansion and the glass transition temperature.
Coefficient of thermal expansion: GB/T36800.2-2018 plastics thermo-mechanical analysis (TMA) part 2: measurement of the coefficient of linear thermal expansion and the glass transition temperature.
Drop impact test: the PCB test sample is a 2X 4 array BGA motherboard, the size is 115mm X77 mm, the thickness is 1.65mm, the substrate FR-4 (epoxy glass cloth laminated board), the pad surface treatment process is HASL, the BGA device is a plastic package PBGA packaging structure, the solder ball spacing is 0.5mm, the chip size is 12mm X0.9 mm, the soldering paste LF300 is soldered in a reflow soldering furnace at room temperature, 50-65% RH and normal pressure. The cofferdam glue prepared by the application example and the comparative application example is dispensed, the width of the glue line is 0.9mm, the height of the glue line is 0.8mm, the length of each L-shaped adhesive tape is 9mm, a substrate is fixed on a base of a drop machine by adopting a clamp of a Lansmont Model 15-D drop test machine, the base is lifted to 1.2m, then the base is allowed to freely fall along a guide rail, each of three X, Y, Z shafts falls once for one cycle, when the total serial resistance of BGA welding spots is more than or equal to 10% before falling, a sample is judged to be invalid, and the number of falling cycles at the moment is recorded.
TABLE 1
From the table above, it can be seen that the cofferdam prepared by the invention has good impact resistance and low thermal linear expansion coefficient under the condition of small decrease of glass transition temperature by adjusting the composition of diisocyanate which is a preparation raw material of branched polyurethane acrylic ester oligomer and the relative dosage of two main resins.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (13)
1. The impact-resistant UV curing cofferdam adhesive is characterized by comprising the following raw materials in parts by weight: 20-25 parts of polyester acrylate oligomer, 10-15 parts of branched polyurethane acrylate oligomer, 5-10 parts of reactive diluent, 40-70 parts of filler, 0.3-1 part of coupling agent, 2.5-4.5 parts of thixotropic agent, 0.1-3 parts of photoinitiator and 0.01-0.03 part of polymerization inhibitor, wherein the branched polyurethane acrylate oligomer is prepared by reacting fluorine-containing dihydric alcohol with diisocyanate to prepare isocyanate-terminated polyurethane oligomer, then reacting the isocyanate-terminated polyurethane oligomer with diethanolamine and dendritic polymer to obtain dendritic polyurethane oligomer, and finally, the dendritic polyurethane oligomer is blocked by an acryloyl chloride compound, and the diisocyanate is prepared by compounding aromatic diisocyanate and aliphatic diisocyanate;
the molar ratio of the diisocyanate, the fluorine-containing dihydric alcohol, the diethanolamine, the dendritic polymer and the acrylic chloride compound is 2.11-2.16:1:0.92-0.95:0.22-0.24:1.84-1.9; the molar ratio of the aromatic diisocyanate to the aliphatic diisocyanate is 1:7-9;
the dendritic polymer is a polypropylene imine dendritic polymer, and the algebra is 1.0 generation; the polypropylene imine dendrimer is selected from one or a combination of two or more of polypropylene imine triamine dendrimer, polypropylene imine diamine dendrimer and polypropylene imine tetramine dendrimer.
2. The impact-resistant UV-curable cofferdam glue of claim 1, wherein the aliphatic diisocyanate is selected from one or more of 1, 6-hexamethylene diisocyanate, decane-1, 10-diisocyanate, trimethylhexamethylene diisocyanate, trimethyl-1, 6-diisocyanatohexane, methylene diisocyanate and lysine ester diisocyanate; the aromatic diisocyanate is selected from one or a combination of two or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -methylene bis (phenyl isocyanate), m-xylylene diisocyanate and p-xylylene diisocyanate.
3. The impact resistant UV curable cofferdam gum of claim 2, wherein the fluorine containing diol has a backbone carbon number of 4-10.
4. An impact resistant UV curable cofferdam gum as claimed in claim 3, wherein, the fluorine-containing diol is selected from octafluoro-1, 6-hexanediol, 2,3, 4-hexafluoro-1, 5-pentanediol 1H, 10H-perfluoro-1, 10-decanediol, 1H, 8H-dodecafluoro-1, 8-octanediol one or two or more of 1H, 9H-perfluoro-1, 9-nonanediol, tetrafluorobutanediol, 2,3, 4-hexafluoro-cyclo-1, 5-pentanediol and 3,3,4,4,5,5,6,6-octafluoro-octane-1, 8-diol.
5. An impact resistant UV curable cofferdam gum as claimed in claim 3, wherein said fluorine containing diol has a backbone carbon number of 8-10.
6. The impact-resistant UV-curable cofferdam glue of claim 1, wherein the acrylic chloride compound is selected from one or a combination of two or more of acrylic chloride, methacrylic chloride and 2-ethyl acrylic chloride.
7. The impact resistant UV curable cofferdam gum of claim 1, wherein said branched urethane acrylate oligomer is made by a process comprising the steps of:
adding diisocyanate and an organic solvent into a reaction kettle under an inert atmosphere, stirring until the diisocyanate and the organic solvent are uniform, heating and keeping the temperature constant, dropwise adding a fluorine-containing dihydric alcohol solution under the stirring condition for reaction, cooling to room temperature after the reaction is finished, and performing column chromatography to obtain an isocyanate-terminated polyurethane oligomer;
under inert atmosphere, dissolving the isocyanate-terminated polyurethane oligomer obtained in the step 1) in an organic solvent, cooling and keeping the temperature, dropwise adding a diethanolamine solution, and carrying out one-step reaction at the constant temperature under the stirring condition; dripping dendritic polymer solution after the reaction is finished, performing two-step reaction at constant temperature, naturally recovering to room temperature after the reaction is finished, and performing column chromatography to obtain dendritic polyurethane oligomer;
under inert atmosphere, dissolving the dendritic polyurethane oligomer obtained in the step 2), an acid binding agent and a stabilizer in an organic solvent, dropwise adding an acryloyl chloride compound solution under the ice water bath condition, reacting at constant temperature, dropwise adding an alkali solution to be neutral after the reaction is finished, and distilling under reduced pressure to obtain the branched polyurethane acrylate oligomer.
8. The impact resistant UV curable cofferdam gum of claim 7, wherein the column chromatography eluent in step 1) is benzene/acetone with a volume ratio of 1-3:1; the temperature of the step 2) is reduced to (-5 ℃) to minus 5 ℃; the eluent for column chromatography is benzene/ethyl acetate 1-3:1.
9. The impact-resistant UV-curable cofferdam glue of claim 1, wherein said polyester acrylate oligomer is prepared by acrylic acid esterification of low molecular weight polyester diol, said polyester acrylate oligomer has a functionality of 2-6 and a viscosity of 2000-20000cP at 25 ℃; the polyester acrylate oligomer is selected from one or a combination of two or more of Photomer 5430, cyanogen EB450, cyanogen EB657, cyanogen EB800, DMI PEAM-645, DMI PEAM-1044, DMI PEM-665, DMI PEAM-1769 and DMI PEM-1066.
10. The impact resistant UV curable cofferdam glue of claim 1, wherein said polyester acrylate oligomer has a functionality of 2-3 and a viscosity of 2000-10000cP at 25 ℃, and is selected from one or a combination of two or more of DMI PEAM-645, DMI PEAM-1044, and DMI PEM-665.
11. The impact-resistant UV-curable cofferdam glue as claimed in claim 1, wherein the filler is silica micropowder, the refractive index is 1.45-1.6, and the particle size is 0.5-10 μm; the thixotropic agent comprises one or a combination of two or more of fumed silica, organic bentonite, hydrogenated castor oil and polyamide wax.
12. The impact resistant UV curable dam adhesive of claim 11, wherein the thixotropic agent is fumed silica having primary particles having an average particle diameter of 5 to 50nm and a specific surface area of 100 to 300m 2 /g。
13. A method of preparing the impact resistant UV curable cofferdam gum as claimed in any one of claims 1-12, comprising the steps of:
adding the polyester acrylate oligomer, the branched polyurethane acrylate oligomer, the reactive diluent, the coupling agent, the photoinitiator and the polymerization inhibitor into a mixer, mixing until uniform, adding the filler and the thixotropic agent, vacuumizing, continuously stirring until uniform, and packaging to obtain the UV curing cofferdam adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211242271.9A CN115449326B (en) | 2022-10-11 | 2022-10-11 | Impact-resistant UV (ultraviolet) curing cofferdam adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211242271.9A CN115449326B (en) | 2022-10-11 | 2022-10-11 | Impact-resistant UV (ultraviolet) curing cofferdam adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115449326A CN115449326A (en) | 2022-12-09 |
| CN115449326B true CN115449326B (en) | 2023-05-19 |
Family
ID=84308201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211242271.9A Active CN115449326B (en) | 2022-10-11 | 2022-10-11 | Impact-resistant UV (ultraviolet) curing cofferdam adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115449326B (en) |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09279076A (en) * | 1996-04-11 | 1997-10-28 | Kansai Paint Co Ltd | Ultraviolet curable ink composition based on urethane acrylate and application film for marking using the same |
| CN1910215B (en) * | 2004-01-14 | 2011-07-06 | 氰特表面技术有限公司 | Adhesives |
| EP1879938B1 (en) * | 2005-05-02 | 2012-04-18 | Cytec Surface Specialties, S.A. | Radiation curable urethane (meth)acrylate polymer and adhesives formulated with them |
| JP5119685B2 (en) * | 2007-02-28 | 2013-01-16 | 東洋インキＳｃホールディングス株式会社 | Urethane resin and method for producing the same, and urethane resin-containing pressure-sensitive adhesive |
| JP4990006B2 (en) * | 2007-04-03 | 2012-08-01 | 株式会社カネカ | Resin blend and its cured product |
| US20090012202A1 (en) * | 2007-07-03 | 2009-01-08 | Henkel Corporation | Acrylated Urethanes, Processes for Making the Same and Curable Compositions Including the Same |
| BRPI0918455A2 (en) * | 2008-09-23 | 2017-05-09 | Cytec Surface Specialties Sa | urethane (meth) acrylate resin, process for preparing a urethane (meth) acrylate resin, radiation curable adhesive composition, method for preparing a radiation cured adhesive, pressure sensitive adhesive |
| JP5418399B2 (en) * | 2009-07-17 | 2014-02-19 | 日立化成株式会社 | Adhesive composition and circuit member connection structure using the adhesive composition |
| JP2011178982A (en) * | 2009-10-21 | 2011-09-15 | Sanko Kagaku Kogyo Kk | Excellent antistatic composition, and molded article, paint, antistatic coating and adhesive containing the same, as well as method of manufacturing the same |
| CN103958532B (en) * | 2011-10-11 | 2018-01-09 | 汉高知识产权控股有限责任公司 | Novel fluorine compound product, its preparation method and by its obtained composition |
| CN105555545B (en) * | 2013-09-18 | 2020-03-03 | 巴斯夫欧洲公司 | Thermal transfer foil for dry coating of surfaces |
| JP6384073B2 (en) * | 2014-03-17 | 2018-09-05 | 東洋インキＳｃホールディングス株式会社 | Active energy ray polymerizable composition, coating agent, and adhesive, and laminate comprising them |
| JP6733153B2 (en) * | 2015-11-17 | 2020-07-29 | セイコーエプソン株式会社 | UV curable composition and recorded matter |
-
2022
- 2022-10-11 CN CN202211242271.9A patent/CN115449326B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115449326A (en) | 2022-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104531041B (en) | Polyether-type urethane acrylate UV-cured adhesive and preparation method thereof | |
| KR101220047B1 (en) | Sealant composition for liquid crystal display device | |
| TW202237673A (en) | Resin composition, adhesive, sealing material, dam agent, and semiconductor device | |
| CN105579477A (en) | Light-/moisture-curable resin composition, electronic component adhesive, and display element adhesive | |
| CN115449326B (en) | Impact-resistant UV (ultraviolet) curing cofferdam adhesive and preparation method thereof | |
| JP4852785B2 (en) | Film adhesive for circuit connection, circuit terminal connection structure, and circuit terminal connection method | |
| WO2018003704A1 (en) | Thermally curable electroconductive adhesive | |
| JP7384168B2 (en) | Semiconductor device manufacturing method and adhesive film for semiconductor wafer processing | |
| CN115386306B (en) | Optical cement, preparation method thereof and related products | |
| JP6523167B2 (en) | Sealant for liquid crystal dropping method, vertical conduction material, and liquid crystal display element | |
| CN115537167B (en) | UV (ultraviolet) curing cofferdam adhesive and preparation method thereof | |
| CN105492480A (en) | Light-/moisture-curable resin composition, electronic component adhesive, and display element adhesive | |
| JPH11269452A (en) | Die attach paste | |
| JP7148799B2 (en) | (Meth)acrylic resin composition and conductive adhesive using the same | |
| JPH11293213A (en) | Production of die attach paste | |
| JP5503134B2 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
| CN117616061A (en) | Curable resin composition | |
| JP4463571B2 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
| JP3209961B2 (en) | Die attach paste | |
| TWI831761B (en) | Curable resin compositions, hardened bodies, electronic parts and assembly parts | |
| JP5067101B2 (en) | Adhesive composition | |
| TW202208480A (en) | Photo/moisture curable resin composition and cured body | |
| CN113801606B (en) | Anisotropic conductive adhesive composition, conductive adhesive film, connector and semiconductor device | |
| WO2022149537A1 (en) | Adhesive composition, adhesive for electronic components, and adhesive for portable electronic devices | |
| CN109370491A (en) | Preparation method of low-surface-energy underfill |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: No.14, Shipai section, Xiangsha Road, Shipai town, Dongguan City, Guangdong Province, 523330 Patentee after: Guangdong Deju Technology Co.,Ltd. Address before: No.14, Shipai section, Xiangsha Road, Shipai town, Dongguan City, Guangdong Province, 523330 Patentee before: CollTech (Dongguan) Bonding Technology Co.,Ltd. |