CN109401706B - High-reliability filling adhesive capable of being rapidly cured - Google Patents
High-reliability filling adhesive capable of being rapidly cured Download PDFInfo
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- CN109401706B CN109401706B CN201811287787.9A CN201811287787A CN109401706B CN 109401706 B CN109401706 B CN 109401706B CN 201811287787 A CN201811287787 A CN 201811287787A CN 109401706 B CN109401706 B CN 109401706B
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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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
- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/08—Epoxidised polymerised polyenes
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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Abstract
The invention relates to filling adhesive and a preparation method thereof, in particular to high-reliability filling adhesive capable of being rapidly cured. The paint is prepared from the following raw materials in percentage by weight: 10-50% of epoxy resin, 5-20% of epoxy diluent, 5-15% of epoxy resin capable of reacting with free radicals, 0-10% of olefin monomer capable of reacting with free radicals, 5-20% of toughening agent, 0.5-3% of coupling agent, 0.1-5% of cationic initiator, 0.1-5% of free radical initiator, 0-50% of filler and 0-5% of pigment. The underfill provided by the invention can be rapidly cured, and has high glass transition temperature (Tg), low expansion coefficient and good reworkability. The method is mainly used for flip chip underfill, and the connection reliability is improved.
Description
Technical Field
The invention relates to filling adhesive and a preparation method thereof, in particular to high-reliability filling adhesive capable of being rapidly cured.
Background
In the world, due to the demands of wireless communication, portable computers, broadband internet products and automobile navigation electronic products, the integration level of electronic components is higher and higher, the chip area is continuously enlarged, the number of pins of integrated circuits is continuously increased, meanwhile, the chip packaging size is required to be further miniaturized and miniaturized, and the integrated circuits are developed towards lighter, thinner and smaller directions, so that a plurality of new packaging technologies and packaging forms appear. Flip chip (flip chip) interconnection technology, which connects an IC chip and a printed wiring substrate by small and thin solder bumps, is one of the most prominent packaging technologies. However, since the thermal expansion coefficients of the chip, the printed wiring board, and the solder are different, thermal stress is likely to occur during a thermal shock test. Particularly, local thermal stress is easily concentrated on the solder bump far from the center of the chip, so that the solder ball is easily cracked, and the performance reliability of the circuit is greatly reduced. Therefore, in order to alleviate the thermal stress, an underfill is formed by the liquid thermosetting resin composition, which can function to protect the chip circuit surface and the solder ball.
The underfill is a one-component liquid encapsulant that is primarily epoxy resin and is typically added with silicon dioxide to increase its strength before it is cured at ambient temperature. One of the main functions of the underfill is to adhere the entire chip to the substrate, or at least along the entire chip edge, to reduce the thermal stress actually applied to the joints, and to adhere the entire chip to the substrate, with the coefficient of linear expansion of the overall composite system between that of the chip and the substrate, thus improving reliability. The gap is typically filled with underfill after the chip is mounted on the PCB substrate, and in the event of a chip failure, the chip needs to be removed from the PCB substrate, the underfill removed, and the chip replaced and remounted. At present, the conventional underfill has the problem of difficulty in repairing and removing the underfill, and particularly, when a thinner circuit board is adopted, the problem of more scrap and the like is easily caused due to weaker thermal damage resistance. Since the rework efficiency of such work is poor, many studies have been made to add a plasticizer or the like to improve the rework efficiency. However, it causes problems such as a decrease in connection reliability and a decrease in curability during thermal cycle treatment due to a decrease in glass transition temperature (Tg), and it is difficult to satisfy the requirements of electronic products in which the use conditions are more and more severe.
Patent CN20151012918.4 mentions that after bismaleimide modified toughened resin and furan alkyl glycidyl ether are crosslinked with main chain, high crosslinking density, high Tg and high rework performance are achieved by means of reversible Diels-Alder reaction between maleimide group and furan end group. However, the Diels-Alder reaction rate between bismaleimide modified toughened resin and furan alkyl glycidyl ether is not high, so that relatively high curing temperature and long curing time are required. With the development of semiconductor integrated circuit technology, the transistor density in a unit area chip is higher and higher, the width of a transistor grid is smaller and smaller, the transistor grid is more and more sensitive to temperature, the failure risk is greatly increased due to long-time high-temperature baking, and the yield of finished products is reduced. In addition, the electronic packaging industry pursues faster assembly efficiency and lower energy consumption cost, and the over-high curing temperature and the over-long curing time cannot completely meet the requirements of the industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the filling adhesive with high reliability and rapid curing and the preparation method thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a high-reliability flip chip underfill capable of being rapidly cured is prepared from the following raw materials in percentage by weight:
10-50% of epoxy resin, 5-20% of epoxy diluent, 5-15% of epoxy resin capable of reacting with free radicals, 0-10% of olefin monomer capable of reacting with free radicals, 5-20% of toughening agent, 0.5-3% of coupling agent, 0.1-5% of cationic initiator, 0.1-5% of free radical initiator, 0-50% of filler and 0-5% of pigment.
In the above scheme, the epoxy resin is one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, dicyclopentadiene phenol type epoxy resin, polyphenol type glycidyl ether epoxy resin, triglycidyl isocyanurate and derivatives thereof;
in the above scheme, the epoxy diluent is one or more of tert-butylphenyl glycidyl ether, cardanol glycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, dimer acid glycidyl ester, dicyclopentadiene diglycidyl dicarboxylate, furan alkyl glycidyl ether, oxetane and derivatives thereof;
wherein, the furan alkyl glycidyl ether has the following structure:
r1 is C1-C5 straight chain alkane, preferably R1 is C1 structure, namely furan methyl glycidyl ether.
In the above scheme, the epoxy resin capable of free radical reaction is one or more of 3, 4-epoxycyclohexyl methyl methacrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, epoxy resin partially modified by (meth) acrylate, epoxidized polybutadiene and epoxy-terminated liquid nitrile rubber ETBN.
In the above scheme, the olefin monomer capable of free radical reaction is one or more of vinyl ether monomer, (meth) acrylic acid (ester) monomer, N-vinyl monomer, acrylamide monomer and allyl monomer.
Further, there may be mentioned ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, cyclohexene vinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, trivinyl glycol divinyl ether, divinyl glycol divinyl ether, butanediol divinyl ether, N-vinyl caprolactam, N-vinyl pyrrolidone, N-acryloyl morpholine, N, N-dimethylacrylamide, isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentadiene (meth) acrylate, ethylene glycol dicyclopentadiene ether (meth) acrylate, dicyclopentadiene di (meth) acrylate, triacrylate isocyanurate, tris (2-hydroxyethyl) isocyanurate triacrylate.
In the scheme, the toughening agent is one or more of polyester polyol, polyether polyol, bismaleimide modified toughening resin and furan methyl glycidyl ether prepolymer.
In the scheme, the bismaleimide modified toughened resin is one or more of bismaleimide modified polyether, bismaleimide modified dimer acid and bismaleimide modified polysiloxane.
Wherein R2 is polyether amine, diamine, amino terminated polysiloxane minus-NH2The residue after;
the structural formula of the polyether amine is as follows:
the structural formula of the polyamines is:
the structural formula of the amino-terminated polysiloxane is as follows:
the bismaleimide modified toughened resin is prepared by carrying out acid forming and dehydration ring-closing reaction on corresponding amino-containing resin and maleic anhydride:
in the scheme, the structural general formula of the bismaleimide modified toughened resin and the furan alkyl glycidyl ether prepolymer is as follows:
wherein R1 and R2 are in accordance with the structure defined above.
In the scheme, the bismaleimide modified toughened resin and furan alkyl glycidyl ether prepolymer is prepared from furan alkyl glycidyl ether and bismaleimide toughened resin, and the specific preparation process is as follows:
the selected dimer amine is prepared from natural oil C18 unsaturated fatty acid, and the molecular structure of the selected dimer amine has two huge C8 alkane branched chains and an alicyclic ring, so that the selected dimer amine has a series of characteristics of low polarity, small crystallinity, good flexibility and the like; meanwhile, polyether amine, di-polyamine and amino-terminated polysiloxane with relatively small molecular weight and poor crystallinity are preferably selected, so that the influence on the viscosity of a system can be reduced, and the reaction activity is ensured;
in the above scheme, the cationic initiator may be a thermal cationic initiator, and specifically may be a thermal sulfonium salt cationic initiator.
In the above scheme, the radical initiator is a thermal radical initiator, and further, the radical initiator is an organic peroxide radical initiator, specifically selected from one or more of alkyl hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate. The self-accelerating decomposition temperature of the organic peroxide radical initiator is preferably less than 160 ℃ and more preferably less than 120 ℃.
In the scheme, the coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N-aminoethyl-3-aminopropylmethyldimethoxysilane.
In the scheme, the filler is spherical silicon micropowder with the particle size of 0.1-10 microns.
In the above scheme, the pigment is one or more of carbon black and titanium black.
A preparation method of the filling adhesive with high reliability and rapid curing comprises the following steps:
(1) weighing 10-50% of epoxy resin, 5-20% of epoxy diluent, 5-15% of epoxy resin capable of reacting with free radicals, 0-10% of olefin monomer capable of reacting with free radicals, 5-20% of toughening agent, 0.5-3% of coupling agent and 0-5% of pigment by weight percentage of the raw materials based on the total weight of the raw materials, putting the raw materials into a reaction kettle, and stirring and mixing the raw materials;
(2) and (3) weighing 0-50% of the filler, adding the filler into the reaction kettle in the step (1) in batches at intervals, and stirring and mixing for 30min after the charging is finished.
(3) And (3) weighing 0.1-5% of cationic initiator and 0.1-5% of free radical initiator, adding into the reaction kettle in the step (2), and stirring for 1-2 hours at the rotating speed of 300-1000 r/min, the temperature of 15-20 ℃ and the vacuum degree of 0.05-0.08 MPa to obtain the finished product.
According to the invention, through the use of the epoxy resin and the epoxy resin capable of free radical reaction, and the matching of the epoxy diluent, the olefin monomer capable of free radical reaction, the flexibilizer, the cationic initiator, the selective addition of the free radical initiator and the like, the control on the fluidity, the curing efficiency and the reliability of the filling adhesive can be achieved, and meanwhile, the repairability is realized by utilizing the resin or the group with the thermal reversible performance.
Specifically, two curing modes of cationic epoxy ring-opening reaction crosslinking and free radical double bond crosslinking are introduced, and the epoxy resin capable of reacting with free radicals is introduced, so that the two curing modes can be further combined. In addition, free radicals generated by the free radical initiator can accelerate the ring opening efficiency of cations of the epoxy group to a certain extent, and further accelerate the curing rate and efficiency; meanwhile, the activation temperatures of the cationic initiator and the free radical initiator are screened, so that lower curing temperature and shorter curing time are realized.
Furthermore, the polyfunctional epoxy resin and the polyfunctional diluent introduced simultaneously can further increase the crosslinking density during curing; in addition, the epoxy resin capable of participating in free radical reaction is introduced, and can simultaneously participate in cationic epoxy ring-opening polymerization and free radical double bond polymerization, so that the crosslinking density is further increased; high glass transition temperature (Tg) is realized, and the reliability requirement is met.
In addition, on the premise of ensuring high Tg, the invention can also realize good repairing performance through a resin or a group with thermal reversibility, such as bismaleimide modified toughened resin prepolymer. Specifically, the furan alkyl glycidyl ether and bismaleimide modified toughened resin prepolymer used in the invention can be decomposed through reverse Diels-Alder reaction at the repair temperature, so that the crosslinking density of the system is reduced. The reaction scheme is shown below. Therefore, the reworking performance of the underfill can be ensured.
Further, the dicyclopentadiene diglycidyl dicarboxylate, dicyclopentadiene di (meth) acrylate or dicyclopentadiene phenol type epoxy resin selected in the present invention can also be decomposed by a reversible reaction at another temperature (rework temperature). The reaction scheme is shown below.
The underfill provided by the invention can be mainly used for flip chip underfill, increases the connection reliability, and has the following beneficial effects:
1. the underfill is prepared by selecting the components of epoxy resin, epoxy diluent, epoxy resin capable of free radical reaction, olefin monomer capable of free radical reaction, toughening agent, coupling agent, cationic initiator, free radical initiator, filler, pigment and the like, and has the characteristics of high glass transition temperature Tg, low expansion coefficient, good connection reliability and quick curing property.
2. The Interpenetrating Polymer Network (IPN) is a polymer blend formed by mutually penetrating and intertwining two or more than two crosslinked polymers through the network, and the system mechanical property of the interpenetrating network polymer is improved.
3. After the bismaleimide modified toughened resin, the furan alkyl glycidyl ether, the bismaleimide modified toughened resin and the furan alkyl glycidyl ether prepolymer are crosslinked with the main chain, a Diels-Alder reaction can be carried out on a maleimide group and a furan end group, the crosslinking density is further polymerized, and the Tg is favorably improved. In addition, the bismaleimide modified toughened resin and the furan alkyl glycidyl ether are used in a prepolymerization mode, so that part of Diels-Alder reaction groups react in advance, the end group of the prepolymer is an epoxy group, the compatibility with a system is good, and the curing efficiency is improved.
4. At the repair temperature, the maleimide and the polymer with the furan end group are subjected to inverse Diels-Alder reaction decomposition, so that the crosslinking density is reduced, the overall bonding performance of the underfill is reduced, and the repair performance is improved; furthermore, epoxy resin containing a dicyclopentadiene structure, a reactive diluent, a monomer and the like are subjected to reverse Diels-Alder reaction chain scission at the repair temperature, so that the repair performance is further improved.
Detailed Description
Epoxy resin:
bisphenol a type epoxy resins available from DER331 (dow chemical), jER828 (mitsubishi chemical), Epikote828 (vandson, the netherlands), NPEL128 (taiwan south asia, china);
bisphenol F type epoxy resins available from DER354 (dow chemical), Epikote862 (vas asia, usa), NPEF170 (taiwan south asia, china);
novolac type epoxy resins available from DEN431, DEN438 (dow chemical), Epikote862 (spain the netherlands);
cycloaliphatic epoxy resins available from CELLOXIDE 2021P, CELLOXIDE EHPE3150 (Daiillol Co., Ltd.), Araldite CY 179 (Henschel, U.S.A.), UVR-6128 (Dow chemical);
dicyclopentadiene phenol type epoxy resins available from KDCP-100, KDCP-150, KDCP-200 (Kyodo chemical), EPICLONE HP-7200 (Dainippon ink);
a glycidyl ether epoxy resin of the polyphenol type, available from Tactix 742 (hensmei, usa), EPALLOY 9000 (CVC, usa);
triglycidyl isocyanurate and derivatives thereof, obtainable from TEPIC, TEPIC-VL (Nissan chemical Co., Ltd.), MA-DGIC, DA-MGIC (four kingdom chemical);
free radical reactive epoxy resin:
3, 4-epoxycyclohexylmethylmethacrylate is available from CYCLOMER M100 (xylonite);
glycidyl Methacrylate ether is available from Glycidyl Methacrylate (dow chemical);
4-hydroxybutylacrylate glycidyl ether is available from 4HBAGE (Mitsubishi chemical);
(meth) acrylate partially modified epoxy resins are available from ETERCURE 6278, ETERCURE 6270 (Changxing Chemicals), EA-1010LC (Xinzhongcun Chemicals);
epoxidized polybutadiene is available from Poly bd 600E, Poly bd 605E, Poly bd 700 (kreviley, france), EPOLEAD PB3600 (xylonite, japan);
the epoxy-terminated liquid nitrile rubber may be obtained from HyproTMETBN (CVC in usa).
The bismaleimide modified toughened resin is prepared by the reaction of corresponding polyether amine, diamine, amino-terminated polysiloxane and maleic anhydride through acid formation and dehydration ring closure.
Polyetheramines, obtainable from
D-230，
D-400 (US Henshimei)
Dipolyamines, obtainable from PriamineTM1071，PriamineTM1074 (great Britain)
Amino-terminated polysiloxanes available from PAM-E, KF-8010, X-22-161 (Nippon Xinyue)
The furan alkyl glycidyl ether is furan methyl glycidyl ether.
The prepolymer is prepared by reacting corresponding bismaleimide modified toughened resin with furan methyl glycidyl ether, and the structural formula of the prepolymer is as follows:
the preparation process of the present invention is further described in detail below with reference to several examples.
Example 1
The raw material components and amounts of underfill provided in examples 1-7 and comparative examples 1-2 are shown in Table 1 below.
In an embodiment of the present invention,
in order to obtain representative data, in the aspect of epoxy resin, the bisphenol A type epoxy resin is selected from Dow DER 331; bisphenol F type epoxy resin selects Dow DER 354; the novolac epoxy resin is Dow DEN 438; the alicyclic epoxy resin is xylonite 2021P; the polyphenol type glycidyl ether epoxy resin is selected from American Hensman Tactix 742; the triglycidyl isocyanurate and its derivative are TEPIC-VL of Nissan chemical, but the invention is not limited thereto.
In order to obtain representative data, in the aspect of epoxy diluent, GS-120 of American CVC is selected as dimer acid glycidyl ester; furan alkyl glycidyl ether is furan methyl glycidyl ether; oxetane and its derivatives are selected from OXT-101 (3-methyl-3-hydroxymethyl oxetane) synthesized in east Asia of Japan, but the present invention is not limited thereto.
To obtainIn the aspect of representative data and toughening agents, the polyester polyol is xylonite polycaprolactone polyol PCL-205U; polyether polyol is selected from American Dow chemical VORANOLTMA CP 450; the bismaleimide modified toughened resin is prepared from Priamine Poa PriamineTM1071 bismaleimide-modified Dipolyamines prepared as starting materials and made by Hensmei, USA
Bismaleimide modified polyether prepared by taking D-230 as a starting material; the bismaleimide modified toughened resin and the furan methyl glycidyl ether prepolymer are prepared from bismaleimide modified polysiloxane prepared by taking Japan shin KF-8010 as an initiator and furan methyl glycidyl ether, and is selected from Priamine of Poa KwangtungensisTM1074 bismaleimide-modified Dipolyamine prepared as a starting material with Furomethylglycidyl Ether the bismaleimide-modified Dipolyamine and Furomethylglycidyl Ether prepolymer is prepared, but the present invention is not limited thereto.
To obtain representative data, the free radically reactive olefinic monomer aspect is a divinyl ether of trivinyl diol selected from the group consisting of basf DVE-3; isobornyl methacrylate is selected from Changxing chemical EM-90; the dicyclopentadiene diacrylate was selected from Sadoma SR-833S, and the tris (2-hydroxyethyl) isocyanurate triacrylate was selected from Yangxing chemical EM-2204, but the present invention is not limited thereto.
To obtain representative data for the free radically reactive epoxy resin, the 3, 4-epoxycyclohexyl methacrylate is selected from the group consisting of xylonite CYCLOMER M100; the epoxidized polybutadiene is selected from Klivirus Poly
605E, but the invention is not limited thereto.
In order to obtain representative data, cationic initiators were selected from the group consisting of the thermal cationic initiators having the following structure:
wherein R3 is hydrogen, methyl, acetyl, methoxycarbonyl, ethoxycarbonyl or benzyloxycarbonyl; r4 and R5 are independently hydrogen, halogen or C1-C4 alkyl; r6 is C1-C4 alkyl; r7 is C1-C4 alkyl, benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, chlorobenzyl, dichlorobenzyl, trichlorobenzyl, nitrobenzyl, dinitrobenzyl, trinitrobenzyl or naphthylmethyl; x is halogen, perchlorate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, alkylsulfonate or p-toluenesulfonate, and also ammonium and phosphorus salts.
SAN-AID SI-300 and SAN-AID SI-B3 of the Japanese Sanxin chemical are further selected, but the invention is not limited thereto.
For representative data, the peroxyester was TriGONOX 21S from Acksonobel (auto-accelerated decomposition temperature of 35 ℃) and the diacyl peroxide was PERKADOX 20S from Acksonobel (auto-accelerated decomposition temperature of 70 ℃) in the case of the free radical initiator, but the invention is not limited thereto.
In order to obtain representative data, gamma-glycidoxypropyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane were used as coupling agents.
The preparation method comprises the following steps:
examples 1-7 and comparative examples 1-2 provide methods for preparing underfill:
1. weighing epoxy resin, epoxy diluent, epoxy resin capable of free radical reaction, olefin monomer capable of free radical reaction, toughening agent, coupling agent and pigment according to the weight percentage of the raw materials in the table 1 in the total weight of the raw materials, putting the raw materials into a reaction kettle, and stirring and mixing the raw materials;
2. weighing the filler, dividing the filler into three equal batches, adding the three equal batches into the reaction kettle in the step 1, wherein the adding time interval of each batch is 15min, and stirring and mixing the materials for 30min after the feeding is finished;
3. weighing a cationic initiator, adding a free radical initiator into the reaction kettle in the step 2, and stirring for 1-2 hours at the rotating speed of 300-1000 r/min, the temperature of 15-20 ℃, the vacuum degree of 0.05-0.08 MPa to obtain a finished product.
Comparative example 1: 20% of bisphenol A epoxy resin, 10% of polyether modified epoxy resin, 10% of furan methyl glycidyl ether, 8% of bismaleimide modified polysiloxane, 10% of bismaleimide modified nitrile rubber, 15% of dicyandiamide, 5% of 2-ethyl-4-methylimidazole, 1.5% of 3-aminopropyltrimethoxysilane, 20% of spherical silicon micropowder and 0.5% of carbon black;
comparative example 2: 20% of bisphenol A epoxy resin, 10% of polyether modified epoxy resin, 10% of 1, 4-butanediol diglycidyl ether, 18% of bismaleimide modified polysiloxane, 15% of dicyandiamide, 5% of 2-ethyl-4-methylimidazole, 1.5% of 3-aminopropyltrimethoxysilane, 20% of spherical silicon micropowder and 0.5% of carbon black;
the underfill provided in the above examples and comparative examples was subjected to the following performance tests: and measuring the viscosity, the flow property and the curing property of the final product, and testing the thermal expansion coefficient, the shear strength and the repairability after curing. The results are shown in Table 2.
1. Viscosity of the oil
The test was carried out using a rotational viscometer at 25 ℃ according to ASTM D2393 test method.
2. Test for curing Properties
Differential Scanning Calorimetry (DSC) was used to obtain a DSC curing curve, in which the temperature rise rate was 60 ℃/min and the curing time in units of min was constant at 120 ℃ curing.
3. Flow property testing method
Using a 24mm by 24mm test piece consisting of a cover glass and a glass slide, the flow time was measured in s at 60 ℃ with a gap of 50 μm (simulating a packaged chip).
4. Coefficient of thermal expansion test (CTE)
Thermomechanical analysis (TMA) was used according to astm d696 standard, with a temperature rise rate of 10 ℃/min in ppm/° c.
5. Glass transition temperature (Tg)
Curing the underfill at 120 ℃ for 30min, testing by thermomechanical analysis (TMA) at a temperature rise rate of 5 ℃/min, and determining the glass transition temperature in units of ℃ during heating from 30 to 300 ℃.
6. Shear strength test
Al/Al shear strength was measured according to ASTM D1002 test method, wherein the curing conditions were 2 hours at 120 ℃ in MPa.
7. Reworkability
A10 x 10mm BGA (0.5mm pitch, 121 pins, 0.35mm diameter solder ball) reflow substrate was used, and the gap between the BGA and the circuit substrate was first filled with underfill, heated at 250 ℃ to dissolve the solder bump joint, and then the BGA was peeled off with a tweezers, and finally the workability was confirmed when removing the composition from the reflow substrate. Good reworkability: the BGA and the underfill are easily removed from the circuit substrate, and the resin on the surface of the circuit substrate is not peeled off; poor reworkability: the BGA and underfill were easily removed from the circuit substrate, but resin peeling occurred from the circuit substrate surface.
TABLE 2
According to the test data in Table 2 above, the underfill of the present invention has the characteristics of fast cure, high glass transition temperature, high shear strength, low linear expansion coefficient, and reworkability. The curing is rapid, the assembly requirement of high-efficiency electronic products is met, and the energy consumption is reduced; high glass transition temperature, high shear strength and low linear expansion coefficient have given the characteristics that underfill high reliability and its can be reprocessed jointly and can make the heating use lower temperature when removing gluey, reduce the thermal damage to mainboard and components and parts from this, and furtherly, it drops from mainboard and components and parts more easily when being heated, can not harm the return circuit base plate to have good reprocessable effect, reprocess the disability rate low.
Claims (8)
1. The utility model provides a high reliability filling glue that can solidify fast which characterized in that: the paint is prepared from the following raw materials in percentage by weight: 10-50% of epoxy resin, 5-20% of epoxy diluent, 5-15% of free-radical reactive epoxy group-containing component, 0-10% of free-radical reactive olefin monomer, 5-20% of toughening agent, 0.5-3% of coupling agent, 0.1-5% of cationic initiator, 0.1-5% of free-radical initiator, 0-50% of filler and 0-5% of pigment;
the toughening agent is a bismaleimide modified toughening resin and furan methyl glycidyl ether prepolymer, and the structural general formula of the toughening agent is as follows:
wherein R is1Is C1-C5 straight chain alkylene,
R2by removal of-NH from polyetheramines, polyamines, amino-terminated polysiloxanes2The residue after;
the structural formula of the polyether amine is as follows:
the structural formula of the polyamines is:
the structural formula of the amino-terminated polysiloxane is as follows:
the compound containing epoxy group capable of free radical reaction is one or more of 3, 4-epoxy cyclohexyl methyl methacrylate, glycidyl methacrylate, 4-hydroxy butyl acrylate glycidyl ether, epoxy resin partially modified by (methyl) acrylate, epoxidized polybutadiene and epoxy-terminated liquid nitrile rubber ETBN.
2. The underfill according to claim 1, wherein: the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, alicyclic epoxy resin, dicyclopentadiene phenol epoxy resin, polyphenol glycidyl ether epoxy resin, triglycidyl isocyanurate and derivatives thereof.
3. The underfill according to claim 1, wherein: the epoxy diluent is one or more of tert-butylphenyl glycidyl ether, cardanol glycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, dimer acid glycidyl ester, dicyclopentadiene diformic acid diglycidyl ester, furan alkyl glycidyl ether, oxetane and derivatives thereof;
wherein, the furan alkyl glycidyl ether has the following structure:
R1is C1-C5 straight chain alkylene.
4. The underfill according to claim 1, wherein: the olefin monomer capable of free radical reaction is one or more of vinyl ether monomer, (methyl) acrylate monomer, N-vinyl monomer, acrylamide monomer and allyl monomer.
5. The underfill according to claim 1, wherein: the radically reactive olefinic monomers are ethyl vinyl ether, N-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, cyclohexene vinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, trivinyl glycol divinyl ether, divinyl glycol divinyl ether, butanediol divinyl ether, N-vinylcaprolactam, N-vinylpyrrolidone, N-acryloylmorpholine, N, N-dimethylacrylamide, isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentadiene (meth) acrylate, ethylene glycol dicyclopentadiene (meth) ether (meth) acrylate, dicyclopentadiene di (meth) acrylate, triallyl isocyanurate, one or more of tris (2-hydroxyethyl) isocyanurate triacrylate.
6. The underfill according to claim 1, wherein: the bismaleimide modified toughened resin is one or more of bismaleimide modified polyether, bismaleimide modified dimer acid and bismaleimide modified polysiloxane, and has a structural general formula:
wherein R is2By removal of-NH from polyetheramines, polyamines, amino-terminated polysiloxanes2The residue after;
the structural formula of the polyether amine is as follows:
the structural formula of the polyamines is:
the structural formula of the amino-terminated polysiloxane is as follows:
7. the underfill according to claim 1, wherein: the cationic initiator is a thermal cationic initiator; the free radical initiator is a thermal free radical initiator, specifically an organic peroxide free radical initiator, and is selected from one or more of alkyl hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide and peroxydicarbonate.
8. The underfill according to claim 1, wherein: the coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N-aminoethyl-3-aminopropylmethyldimethoxysilane; the filler is spherical silicon micro powder with the particle size of 0.1-10 mu m; the pigment is one or more of carbon black and titanium black.
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| CN111234713A (en) * | 2019-05-29 | 2020-06-05 | 深圳市鑫东邦科技有限公司 | Underfill adhesive and preparation method thereof |
| CN110894295B (en) * | 2019-10-23 | 2021-11-02 | 广东同宇新材料有限公司 | Polyether maleimide resin and synthetic method thereof |
| CN111073522A (en) * | 2019-12-04 | 2020-04-28 | 络合高新材料(上海)有限公司 | Special epoxy adhesive for bonding UV (ultraviolet) photocuring PVC (polyvinyl chloride) base materials |
| CN112375524B (en) * | 2020-11-06 | 2022-11-22 | 深圳市晨日科技股份有限公司 | Epoxy glue and preparation method and application thereof |
| WO2023223927A1 (en) * | 2022-05-17 | 2023-11-23 | Dic株式会社 | Glycidyl ether group-containing compound, curable resin composition, cured product, and laminate |
| CN114958262B (en) * | 2022-06-30 | 2023-11-10 | 烟台德邦科技股份有限公司 | Chip-level underfill adhesive based on biological base and suitable for large-size chip packaging and preparation method |
| CN115521691A (en) * | 2022-10-31 | 2022-12-27 | 重庆邦锐特新材料有限公司 | UV cationic free radical hybrid curing adhesive and preparation method and application thereof |
| CN115820181A (en) * | 2022-12-07 | 2023-03-21 | 东莞市新懿电子材料技术有限公司 | Underfill adhesive based on composite nano filler and preparation method and application thereof |
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