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CN115449326A - 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 PDF

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Publication number
CN115449326A
CN115449326A CN202211242271.9A CN202211242271A CN115449326A CN 115449326 A CN115449326 A CN 115449326A CN 202211242271 A CN202211242271 A CN 202211242271A CN 115449326 A CN115449326 A CN 115449326A
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diisocyanate
cofferdam
oligomer
acrylate oligomer
impact
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CN115449326B (en
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罗勇
黄成生
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Guangdong Deju Technology Co ltd
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Colltech Dongguan Bonding Technology Co ltd
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    • 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

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  • 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-cured cofferdam glue and a preparation method thereof, wherein the preparation method comprises the following raw materials: the branched polyurethane acrylate oligomer is prepared by the steps of firstly 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 terminating the dendritic polyurethane oligomer by an acryloyl chloride compound, wherein the diisocyanate is prepared by compounding aromatic diisocyanate and aliphatic diisocyanate. According to the invention, by adjusting the composition of the diisocyanate used as the raw material for preparing the branched polyurethane acrylate oligomer and the relative amounts of the two main resins, the cofferdam rubber has good impact resistance and low thermal linear expansion coefficient under the condition of not reducing the glass transition temperature.

Description

Impact-resistant UV (ultraviolet) curing cofferdam adhesive and preparation method thereof
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 and mechanical stresses are the main causes of failure of integrated circuit structures, and most of the failure occurs at the joint of a chip and a circuit board, which is composed of a large number of tiny-sized pads, which have small deformation adaptability and are sensitive to thermal and mechanical stresses, so that the reliability problem of the integrated circuit is more prominent.
The underfill is a technology for improving the working stability and reliability of electronic products in severe environments, can effectively reduce impact load and thermal load, can also improve the deformation resistance, chemical corrosion resistance and other properties of the packaged chip, and can greatly improve the fatigue life of the packaged chip, thereby having great development potential. The bottom filling mode comprises bottom complete filling and four-corner peripheral filling, the glue used for the bottom complete filling is called bottom filling glue, and the glue used for the four-corner peripheral filling is called cofferdam glue, box dam glue or four-corner binding glue. Because the two kinds of glue are different in use position, the two kinds of glue have great difference in performance: the underfill requires that the glue has good fluidity so that the glue can fill the bottom of the chip quickly by using the capillary effect of the liquid; the cofferdam glue needs to have good thixotropy, so that the glue is not easy to flow, the movement after the glue dispensing is very small, and the situation that elements which do not need to be filled are filled or the buckling shielding cover is influenced is avoided. The underfill is too long in underfill time, the underfill process is obviously affected by 'edge effect', the underfill degree is low, the protection function of welding spots is weakened, and the cofferdam glue becomes a key research and development object of current researchers, for example, patents CN201410795290.3, CN201710294375.7, LOCTITE3128 and LOCTITE3128NH of LOCTITE, and 9422-SC and 9309-SC of DYMAX are cofferdam glues, wherein 9422-SC and 9309-SC of DYMAX are two novel UV-cured acrylic polyurethane cofferdam glues, and have the advantages of fast curing speed compared with the conventional silicone type and epoxy type cofferdam glues, capability of completing curing within several seconds to twenty seconds, suitability for industrial continuous automatic production of integrated circuits, but the two UV-cured acrylic polyurethane cofferdam glues have low crosslinking degree, low glass transition temperature, and low temperature between 60 ℃ and 70 ℃, when the temperature of the integrated circuits is higher than Tg, or the thermal expansion coefficient increases, the dropping, the two UV-cured acrylic polyurethane type cofferdam glues are suitable for being applied to outdoor vibration protection of portable electronic devices, and electronic book communication equipment, and the like.
In conclusion, the development of the UV curing cofferdam adhesive with impact resistance, low thermal expansion coefficient and high glass transition temperature has great significance for expanding the application of the cofferdam adhesive in portable electronic equipment and electronic equipment working in severe environment.
Disclosure of Invention
In order to solve the problems, the invention provides the anti-impact UV curing cofferdam glue and the preparation method thereof, the main resin of the cofferdam glue comprises polyester acrylate oligomer and branched polyurethane acrylate oligomer, and the cofferdam glue has good anti-impact performance and low thermal linear expansion coefficient under the condition that the glass transition temperature is not reduced greatly by adjusting the composition of diisocyanate which is a raw material prepared from the branched polyurethane acrylate oligomer and the relative dosage of the two main resins.
In order to realize the purpose, the following specific technical scheme is adopted:
an impact-resistant UV-cured cofferdam adhesive comprises the following raw materials: the polyurethane acrylate oligomer is prepared by the two-step reaction of isocyanate terminated polyurethane oligomer prepared by the reaction of fluorine-containing dihydric alcohol and diisocyanate, diethanolamine and dendritic polymer to obtain dendritic polyurethane oligomer, and the dendritic polyurethane oligomer is terminated by acryloyl chloride compounds, wherein the diisocyanate is prepared by compounding aromatic diisocyanate and aliphatic diisocyanate.
Further, the anti-impact UV curing cofferdam glue 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 acryloyl 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.
The aliphatic diisocyanate is selected from one or the 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 trimethyl hexamethylene diisocyanate.
The aromatic diisocyanate is one or the 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.
<xnotran> 4-10, -1,6- ,2,2,3,3,4,4- -1,5- ,1H,1H,10H,10H- -1,10- ,1H,1H,8H,8H- -1,8- ,1H,1H,9H,9H- -1,9- , ,2,2,3,3,4,4- -1,5- ,3,3,4,4,5,5,6,6- -1,8- . </xnotran>
<xnotran> , 8-10, 1H,1H,10H,10H- -1,10- ,1H,1H,8H,8H- -1,8- ,1H,1H,9H,9H- -1,9- ,3,3,4,4,5,5,6,6- -1,8- . </xnotran>
The dendritic polymer is a polypropylene imine dendritic polymer, and the generation number is 1.0 generation; the polypropylene imine dendrimer comprises one or the combination of two or more of polypropylene imine triamine dendrimer, polypropylene imine diamine dendrimer and polypropylene imine tetramine dendrimer.
The acryloyl chloride compound is one or a combination of two or more of acryloyl chloride, methacryloyl chloride and 2-ethyl acryloyl chloride, and is preferably methacryloyl chloride.
The branched urethane acrylate oligomer is prepared by a method comprising the following steps:
4) Under the inert atmosphere, adding diisocyanate and an organic solvent into a reaction kettle, stirring uniformly, heating and keeping constant temperature, 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 isocyanate-terminated polyurethane oligomer;
5) Dissolving the isocyanate-terminated polyurethane oligomer obtained in the step 1) in an organic solvent in an inert atmosphere, cooling and keeping the temperature constant, dropwise adding a diethanolamine solution, and carrying out one-step reaction at the constant temperature under the stirring condition; after the reaction is finished, dropwise adding the dendritic polymer solution, carrying out two-step reaction at constant temperature, naturally returning to room temperature after the reaction is finished, and carrying out column chromatography to obtain a dendritic polyurethane oligomer;
6) Dissolving the dendritic polyurethane oligomer obtained in the step 2), an acid-binding agent and a stabilizer in an organic solvent in an inert atmosphere, dropwise adding an acryloyl chloride compound solution under the ice-water bath condition, reacting at constant temperature, dropwise adding alkali liquor 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 the combination of two or more of DMF, DMSO, acetonitrile, acetone, ether, benzene and xylene; the temperature is raised to 40-80 ℃, and the concentration of the fluorine-containing glycol solution is 10-30wt%; the stirring speed is 300-500r/min, the dropping speed of the fluorine-containing glycol solution is 0.5-1 drop/s, the reaction time is 1-5h, the column chromatography eluent is benzene/acetone, and the volume ratio is 1-3.
Step 2), the temperature is reduced to (-5 ℃) to-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. And 2) controlling the temperature at a low temperature section by utilizing different reactivity of hydroxyl, amino and isocyanic acid radical, so that the amino and the isocyanic acid radical react, and the hydroxyl and the isocyanic acid radical do not react to prepare the dendritic polyurethane oligomer.
The catalyst in the step 3) is selected from one or a combination of two or more of triethylamine, triethylenediamine and N, N-dimethylcyclohexylamine, the molar ratio of the acid-binding agent to the acryloyl chloride compound is 1.84-1.9, the stabilizer is selected from one or a combination of two or more of hydroquinone, p-methoxyphenol and 2, 6-di-tert-butyl-p-cresol, the dosage of the stabilizer is 0.1-0.5wt% of the acryloyl chloride compound, the concentration of the acryloyl chloride compound solution is 5-10wt%, the concentration of the acryloyl chloride compound solution is 20-60min after dripping, the constant temperature reaction time is 1-3h, the organic solvent is the same as the organic solvent in the step 1), the alkali liquor is not particularly limited, and one or a combination of saturated sodium hydroxide solution and sodium bicarbonate solution in the field is commonly used.
The polyester acrylate oligomer is obtained by acrylating low molecular weight polyester diol, the functionality of the polyester acrylate 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, cyanote EB450, cyanote EB657, cyanote EB800, DMI PEAM-645, DMI PEAM-1044, DMI PEM-665, DMI PEAM-1769 and DMI PEM-1066.
Preferably, the functionality of the polyester acrylate oligomer is 2-3, the viscosity is 2000-10000cP (25 ℃), and the polyester acrylate oligomer 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 acrylate oligomer DMI PEAM-645 is a low-viscosity oligomer, the molecular main chain comprises a structural unit formed by tricyclo [5.2.1.0,2,6] decane dimethanol and isophthalic acid, and the oligomer molecules are rigid, so that the cofferdam glue formed by the oligomer has higher glass transition temperature and lower low thermal linear expansion coefficient.
The reactive diluent is not particularly limited, and may be one or a combination of two or more selected from the group consisting of isobornyl acrylate, cyclohexyl methacrylate, dicyclopentadiene methacrylate, isobornyl methacrylate, methacrylic acid, and dicyclopentadiene acrylate, as is commonly used in the art.
The filler is silicon micropowder with the refractive index of 1.45-1.6 and the particle size of 0.5-10 mu m.
The silicon micropowder is selected from one or more of SF102, SF106, SF202, SF210, SF400 and SF600 of Shanghai good Zhen industry, and Sc2500SMJ and SC5500SMJ of Japan.
The coupling agent is one or the 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 the combination of two or more of fumed silica, organic bentonite, hydrogenated castor oil and polyamide wax.
Preferably, the thixotropic agent is fumed silica, the fumed silica havingThe primary particles have an average particle diameter of 5-50nm and a specific surface area of 100-300m 2 /g。
The fumed silica is selected from one or a combination of two or more of Yingchuang R202, R974, wacker H18, H15, kabot TS620 and TS 720.
The initiator is a cracking type free radical photoinitiator, is selected from one or a combination of two or more of benzoin initiators, alpha-hydroxy ketone initiators, alpha-amino ketone initiators and acyl phosphine oxide initiators, 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 one or the combination of two or more of hydroquinone, p-methoxyphenol and 2, 6-di-tert-butyl-p-cresol.
The UV curing cofferdam glue also can comprise 0.05-0.2 part of dispersant and 0.1-0.5 part of defoamer.
The dispersing agent is selected from one or a combination of two or more of BYK110, BYK163, BYK9010 and BYK 9076.
The defoaming agent is selected from one or a combination of two or more of BYK 088, BYK 080A and TEGO 3062.
The invention also provides a preparation method of the UV curing cofferdam glue, which comprises the following steps:
adding polyester acrylate oligomer, branched polyurethane acrylate oligomer, reactive diluent, coupling agent, photoinitiator and polymerization inhibitor into a mixer, mixing uniformly, adding filler and thixotropic agent, vacuumizing, continuously stirring uniformly, and packaging to obtain the UV-cured cofferdam adhesive.
An application method of UV curing cofferdam glue comprises the steps of enabling the UV curing cofferdam glue to be dripped on the periphery of four corners of an electronic element through a glue dispenser, and then curing the UV curing cofferdam glue through ultraviolet illumination.
The power of the ultraviolet light is 100-300mW/cm 2 The illumination time is 10-60s, and the illumination lamp distance is 10-40cm.
The width of the glue line is 0.5-5mm and the height of the glue line is 0.5-3mm after the glue dispensing of the glue dispenser.
The dispensing path of the dispenser is selected from one of a linear type or an L type.
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 cofferdam glue has good impact resistance and low thermal linear expansion coefficient under the condition that the glass transition temperature is not reduced greatly by adjusting the composition of diisocyanate serving as a raw material for preparing the branched polyurethane acrylate oligomer and the relative dosage of the two main resins.
The preparation method is simple, green and environment-friendly, and is suitable for industrial production.
Drawings
FIG. 1 is a thermomechanical profile of an impact-resistant UV dam adhesive prepared in application example 1;
fig. 2 is a photograph of the impact-resistant UV dam gum prepared in application example 1 after curing by dispensing.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the descriptions in the following. Unless otherwise specified, "parts" in the examples of the present invention are parts by weight. All reagents used are commercially available in the art.
Polypropyleneimine diamine dendrimers 1.0 are available from Nanjing Skyo Biotech, inc.,
polypropyleneiminotriamine dendrimer 1.0 is available from Biotech, inc., nanjing Shimadzu.
DMI PEAM-645 and DMI PEAM-665 are both available from Designer Molecules Inc.
Cyanote EB800 was purchased from Cyanote corporation, USA.
Preparation of branched urethane acrylate oligomer
Preparation example 1
1) Under nitrogen atmosphere, 0.216mol of diisocyanate prepared by mixing 2, 4-toluene diisocyanate and 1, 6-hexamethylene diisocyanate according to a molar ratio of 1.
2) Under the atmosphere of nitrogen, 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 a diethanolamine solution (the solvent is DMF) with the concentration of 10wt%, dropping for 20min, carrying out a one-step reaction for 2h at the rotation speed of 300r/min and keeping the constant temperature, dropwise adding 63.5g of a 1.0 generation solution (the solvent DMF) of a 10wt% polypropyleneimine diamine dendrimer with the concentration of 10wt% after the reaction is finished, dropping for 30min, carrying out a two-step reaction for 2h at the rotation speed of 300r/min and keeping the constant temperature, naturally returning to the room temperature after the reaction is finished, and carrying out column chromatography separation to obtain the dendritic polyurethane oligomer, wherein the eluent is obtained by mixing benzene/ethyl acetate according to the volume ratio of 2.
3) Under the atmosphere of nitrogen, dissolving the dendritic polyurethane oligomer obtained in the step 2), 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 methacryloyl chloride solution (solvent DMF) with the concentration of 5wt% under the condition of ice-water bath, reacting for 30min, reacting for 1h at constant temperature, dropwise adding saturated sodium bicarbonate solution to neutrality after the reaction is finished, and distilling under reduced pressure to obtain the branched polyurethane acrylate oligomer.
Preparation example 2
The procedure was repeated as in preparation example 1 except that the diisocyanate was prepared by mixing 2, 4-tolylene diisocyanate and 1, 6-hexamethylene diisocyanate in a molar ratio of 1.
Preparation example 3
The procedure was repeated as in preparation example 1 except that the diisocyanate was prepared by mixing 2, 4-tolylene diisocyanate and 1, 6-hexamethylene diisocyanate in a molar ratio of 1.
Preparation example 4
The procedure was repeated as in preparation example 1 except that the diisocyanate was prepared by mixing 2, 4-tolylene diisocyanate and 1, 6-hexamethylene diisocyanate in a molar ratio of 1.
Preparation example 5
The procedure was as in preparation example 1, except that 1, 6-hexamethylene diisocyanate was replaced with an equimolar amount of trimethylhexamethylene diisocyanate.
Preparation example 6
The procedure was as in preparation example 1, except that 2, 4-tolylene diisocyanate was replaced with an equimolar amount of 4,4' -methylenebis (phenylisocyanate).
Preparation example 7
The procedure was as in preparation example 1 except that the octafluoro-1, 6-hexanediol solution was used in an equimolar amount instead of 1H, 10H-perfluoro-1, 10-decanediol.
Preparation example 8
The procedure was as in preparation example 1 except that 1, 6-hexamethylene diisocyanate was replaced with an equimolar amount of methylene diisocyanate.
Preparation example 9
The procedure was repeated except that 2, 4-tolylene diisocyanate and 1, 6-hexamethylene diisocyanate were mixed in a molar ratio of 1.
Comparative preparation example 1
The procedure was as in preparation example 1, except that the diisocyanate contained no 1, 6-hexamethylene diisocyanate and that 0.216mol of the diisocyanate consisted entirely of 2, 4-tolylene diisocyanate.
Preparation of impact-resistant UV-cured cofferdam rubber
Example 1
Adding 25 parts of DMI PEAM-645, 15 parts of the branched polyurethane acrylate oligomer prepared in preparation example 1, 3 parts of dicyclopentadiene acrylate, 3 parts of methacrylic acid, 1 part of gamma-glycidyl ether oxypropyltrimethoxysilane, 2 parts of Irgacure184, 0.2 part of Irgacure TPO, 0.8 part of Irgacure819 and 0.01 part of hydroquinone into a mixer, mixing uniformly, adding 48.8 parts of SC5500SMJ and 4.5 parts of carbopt TS720, vacuumizing, continuously stirring uniformly, and packaging to obtain the UV curing cofferdam adhesive.
Examples 2 to 9
The same as in example 1 except that the branched urethane acrylate oligomer was used as prepared in accordance with preparation examples 2 to 9, respectively.
Example 10
The procedure was repeated as in example 1 except that DMI PEAM-645 was used in an amount of 20 parts and that the branched urethane acrylate oligomer prepared in preparation example 1 was used in an amount of 10 parts.
Comparative example 1
The same as example 1 except that the branched urethane acrylate oligomer used was prepared as in comparative example 1.
Application example 1
Dispensing the UV-cured cofferdam glue prepared in the embodiment 1 on the periphery of four corners of a chip with the thickness of 15mm multiplied by 20mm on a hard PCB by an L-shaped dispensing path by using a Cedren SEC-DP300 dispenser, wherein the width of a glue line is 2.5mm, the height of the glue line is 2mm, and then dispensing is carried out at the power of 100mW/cm 2 Is irradiated for 60s under an ultraviolet lamp with a lamp distance of 20cm.
Application examples 2 to 10, comparative application example 1
The same as in application example 1 except that UV-curable dam paste was used in accordance with examples 2 to 10 and comparative example 1.
The UV curing cofferdam glue prepared by the application examples 1-10 and the comparative application example 1 is subjected to the following performance tests:
before curing
Thixotropic coefficient: and (3) testing the viscosity of the same rotor at 5rpm and 50rpm respectively by using a rotational viscometer, wherein the ratio of the two is the thixotropic coefficient.
Viscosity: the measurement was carried out using a rotary viscometer at 25 ℃.
Curing speed: the ultraviolet curing machine is a Shenzhen Shennede photoelectric technology Limited company, 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 tested according to ASTM D2240.
After curing
Glass transition temperature: GB/T36800.2-2018 thermo-mechanical analysis of plastics (TMA) part 2: measurement of linear thermal expansion coefficient and glass transition temperature.
Coefficient of thermal expansion: GB/T36800.2-2018 thermo-mechanical analysis of plastics (TMA) part 2: measurement of linear thermal expansion coefficient and glass transition temperature.
And (3) drop impact resistance test: the PCB sample is a 2 x 4 array BGA mainboard, the size is 115mm x 77mm, the thickness is 1.65mm, a substrate FR-4 (epoxy glass cloth laminated board), the surface treatment process of a bonding pad is HASL, the BGA device is a plastic package PBGA package structure, the solder ball interval is 0.5mm, the chip size is 12mm x 0.9mm, and the soldering paste LF300 is welded in a reflow furnace at room temperature, 50-65% RH and normal pressure. Dispensing with cofferdam glue prepared by an application example and a comparative application example respectively, wherein the width of the glue line is 0.9mm, the height of the glue line is 0.8mm, the length of each L-shaped glue strip is 9mm, fixing the substrate on a base of a falling machine by a fixture for a Lansmont Model 15-D falling tester, lifting the base by 1.2m, then enabling the base to freely fall along a guide rail, enabling the X axis, the Y axis and the Z axis to respectively fall once for one cycle, judging that a sample is invalid when the total series resistance ratio of BGA welding spots is more than or equal to 10% before falling, and recording the number of the falling cycles at the moment.
TABLE 1
Figure BDA0003885223110000091
The above table shows that the cofferdam gum prepared by the invention has good impact resistance and low thermal linear expansion coefficient under the condition that the glass transition temperature of the cofferdam gum is not reduced greatly by adjusting the composition of diisocyanate which is a raw material for preparing the branched urethane acrylate oligomer and the relative amount of the two main resins.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.

Claims (10)

1. The impact-resistant UV-cured cofferdam glue is characterized by comprising the following raw materials: the polyurethane-acrylate composite material comprises a polyester acrylate oligomer, a branched polyurethane acrylate oligomer, a reactive diluent, a filler, a coupling agent, a thixotropic agent, a photoinitiator and a polymerization inhibitor, wherein the branched polyurethane acrylate oligomer is prepared by reacting fluorine-containing dihydric alcohol with diisocyanate to prepare an isocyanate-terminated polyurethane oligomer, then reacting the isocyanate-terminated polyurethane oligomer with diethanolamine and a dendritic polymer to obtain a dendritic polyurethane oligomer, and finally terminating the dendritic polyurethane oligomer by an acryloyl chloride compound, wherein the diisocyanate is prepared by compounding aromatic diisocyanate and aliphatic diisocyanate.
2. The impact-resistant UV-curing cofferdam glue of claim 1 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 molar ratio of the diisocyanate, the fluorine-containing diol, the diethanolamine, the dendritic polymer and the acryloyl 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.
3. The impact-resistant UV-curable cofferdam gum of claim 1, wherein said aliphatic diisocyanate is selected from one or a combination of two or more of 1, 6-hexamethylene diisocyanate, decane-1, 10-diisocyanate, trimethylhexamethylene diisocyanate, trimethyl-1, 6-diisocyanatohexane, methylene diisocyanate, 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 trimethyl hexamethylene diisocyanate; the aromatic diisocyanate is selected from one or the 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;
<xnotran> , 4-10, -1,6- ,2,2,3,3,4,4- -1,5- ,1H,1H,10H,10H- -1,10- ,1H,1H,8H,8H- -1,8- ,1H,1H,9H,9H- -1,9- , ,2,2,3,3,4,4- -1,5- ,3,3,4,4,5,5,6,6- -1,8- ; </xnotran> <xnotran> , 8-10, 1H,1H,10H,10H- -1,10- ,1H,1H,8H,8H- -1,8- ,1H,1H,9H,9H- -1,9- ,3,3,4,4,5,5,6,6- -1,8- . </xnotran>
4. The impact-resistant UV-curable cofferdam gum of claim 1, wherein said dendritic polymer is a polypropyleneimine dendrimer, the generation number is 1.0; the polypropylene imine dendrimer comprises one or the combination of two or more of polypropylene imine triamine dendrimer, polypropylene imine diamine dendrimer and polypropylene imine tetramine dendrimer; the acryloyl chloride compound is one or a combination of two or more of acryloyl chloride, methacryloyl chloride and 2-ethyl acryloyl chloride, and is preferably methacryloyl chloride.
5. The impact-resistant UV-curable cofferdam gum of claim 1, wherein said branched urethane acrylate oligomer is prepared by a process comprising the steps of:
1) Under the inert atmosphere, adding diisocyanate and an organic solvent into a reaction kettle, stirring uniformly, heating and keeping constant temperature, 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 isocyanate-terminated polyurethane oligomer;
2) Dissolving the isocyanate-terminated polyurethane oligomer obtained in the step 1) in an organic solvent in an inert atmosphere, cooling and keeping the temperature constant, dropwise adding a diethanolamine solution, and carrying out one-step reaction at the constant temperature under the stirring condition; after the reaction is finished, dropwise adding the dendritic polymer solution, carrying out two-step reaction at constant temperature, naturally returning to room temperature after the reaction is finished, and carrying out column chromatography to obtain a dendritic polyurethane oligomer;
3) Under an 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 an ice-water bath condition, reacting at a constant temperature, dropwise adding alkali liquor to be neutral after the reaction is finished, and distilling under reduced pressure to obtain the branched polyurethane acrylate oligomer.
6. The anti-impact UV-curing cofferdam gum of claim 1, wherein the column chromatography eluent of step 1) is benzene/acetone in a volume ratio of 1-3; step 2), the temperature is reduced to (-5 ℃) to-5 ℃; the eluent for column chromatography is benzene/ethyl acetate 1-3.
7. The impact-resistant UV-curable cofferdam gum of claim 1, wherein said polyester acrylate oligomer is obtained by acrylating a low molecular weight polyester diol, said polyester acrylate oligomer having a functionality of 2 to 6 and a viscosity of 2000 to 20000cP (25 ℃); the polyester acrylate oligomer is selected from one or a combination of two or more of Photomer 5430, cyanotex EB450, cyanotex EB657, cyanotex EB800, DMI PEAM-645, DMI PEAM-1044, DMI PEM-665, DMIPEAM-1769 and DMI PEM-1066.
8. The impact resistant UV cured cofferdam gum of claim 1, wherein said polyester acrylate oligomer has a functionality of 2-3 and a viscosity of 2000-10000cP (25 ℃), one or a combination of two or more selected from the group consisting of DMI PEAM-645, DMI PEAM-1044, and DMI PEM-665; preferably, the polyester acrylate oligomer is DMIPEAM-645.
9. The impact-resistant UV-cured cofferdam gum of claim 1, wherein the filler is silica micropowder with a refractive index of1.45-1.6, the grain diameter is 0.5-10 μm; the thixotropic agent comprises one or the combination of two or more of fumed silica, organic bentonite, hydrogenated castor oil and polyamide wax; preferably, the thixotropic agent is fumed silica, the average particle diameter of primary particles of the fumed silica is 5-50nm, and the specific surface area is 100-300m 2 /g。
10. The process for preparing an impact resistant UV curable cofferdam gum as claimed in any one of claims 1-9, comprising the steps of:
adding polyester acrylate oligomer, branched polyurethane acrylate oligomer, reactive diluent, coupling agent, photoinitiator and polymerization inhibitor into a mixer, mixing uniformly, adding filler and thixotropic agent, vacuumizing, continuously stirring uniformly, and packaging to obtain the UV curing cofferdam adhesive.
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