CN114196361B - Adhesive with high temperature, high adhesive strength and low viscosity and preparation method thereof - Google Patents
Adhesive with high temperature, high adhesive strength and low viscosity and preparation method thereof Download PDFInfo
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- CN114196361B CN114196361B CN202111669813.6A CN202111669813A CN114196361B CN 114196361 B CN114196361 B CN 114196361B CN 202111669813 A CN202111669813 A CN 202111669813A CN 114196361 B CN114196361 B CN 114196361B
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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
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
- C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic containing oxygen in the form of ether bonds in the main chain
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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Abstract
The invention discloses an adhesive with high temperature, high bonding strength and low viscosity and a preparation method thereof, and relates to an adhesive and a preparation method thereof. Solves the problem that the electronic adhesive used in the prior rapid dispensing and glue spraying processes is difficult to achieve both low viscosity and high-temperature high-adhesion strength. The adhesive with high temperature, high adhesion strength and low viscosity is prepared from epoxy resin, bismaleimide resin containing a Cardo ring structure, a curing agent, an initiator, an inorganic filler and a solvent; the preparation method comprises the following steps: 1. preparing bismaleimide resin containing a Cardo ring structure; 2. weigh and mix.
Description
Technical Field
The invention relates to an adhesive and a preparation method thereof.
Background
With the rapid development of the microelectronic packaging industry, microelectronic packaging technologies have been given higher demands, such as smaller overall dimensions, higher density, better mechanical and electrical connection performance, longer product life, etc. of packaged products. The manufacturing process, the service performance and the application of the electronic package basically depend on various materials constituting the package, and the processability, the physical properties (such as resistivity, dielectric constant, thermal conductivity, thermal expansion coefficient and the like), the compatibility, the cost and the like of the materials need to be comprehensively considered. Among these, the role played by the encapsulation of the connection material is critical. The packaging connection material connects packaging structures of different levels, mainly plays roles of electric, mechanical connection, signal transmission and the like, and the electronic adhesive is the most widely used packaging connection material.
Electronic adhesives generally have the functions of bonding, potting, sealing, underfilling, dam coating, shape coating and conducting in electronic products, and to achieve this, it is first ensured that the electronic adhesive can be stably, efficiently and accurately distributed to a suitable position, and the most commonly used is a dispensing process. Among these, the most widely used is contact dispensing and non-contact spray dispensing, and in order to improve the dispensing efficiency, high-speed dispensing is often required.
The high-speed dispensing has higher viscosity requirement on the adhesive, and has lower dynamic viscosity on the premise of keeping certain thixotropic property of the adhesive, and when the viscosity of the adhesive exceeds a certain range, the dispensing efficiency is reduced, and the needle is easy to be blocked. For the use process of high-speed dispensing, corresponding electronic adhesive products are developed by various manufacturers at present, and the common problem of the products is that the adhesive strength is low, especially the adhesive strength at high temperature is greatly reduced, which is very unfavorable for components and parts subjected to high-temperature reflow soldering and other severe environments. This is mainly because the current way of reducing the viscosity of electronic adhesives is limited, mainly by the addition of solvents or reactive diluents. The former not only causes defects due to solvent volatilization during curing, which leads to the decrease of the bonding strength of the element or the falling off, but also can cause the phase separation of a resin system due to the solubility problem of part of the resin, and also causes defects during curing; the latter often results in a substantial decrease in the strength of the overall system at high temperatures due to the large number of soft segments introduced by the diluent. On the other hand, the traditional high-strength electronic adhesive often adopts an aromatic heterocyclic resin system and a rubber toughening system. The introduction of a large amount of aromatic heterocyclic resin can obviously improve the thermal mechanical property of the material, and can maintain certain strength under the high-temperature condition, but also brings higher viscosity to the system, so that the aromatic heterocyclic resin is difficult to be applied to high-speed dispensing; while the rubber toughening system can well enhance the bonding strength at room temperature, the improvement of the bonding strength at high temperature is very limited.
Therefore, a new resin system is developed to be applied to the electronic adhesive, so that the electronic adhesive can be used for both low-viscosity high-speed dispensing and high-temperature high-adhesion strength, and has great research significance for the electronic packaging industry.
Disclosure of Invention
The invention aims to solve the problem that the electronic adhesive used in the existing quick dispensing and glue spraying processes is difficult to achieve both low viscosity and high-temperature high-adhesion strength, and provides an adhesive with high-temperature high-adhesion strength and low viscosity and a preparation method thereof.
The adhesive with high temperature, high adhesion strength and low viscosity is prepared from 100 parts of epoxy resin, 5-20 parts of bismaleimide resin containing a Cardo ring structure, 10-100 parts of curing agent, 0.1-0.5 part of initiator, 100-800 parts of inorganic filler and 0-15 parts of solvent according to parts by weight;
the monomer structural formula of the bismaleimide resin containing the Cardo ring structure is as follows:
said R is 1 Is that
The preparation method of the adhesive with high temperature, high bonding strength and low viscosity comprises the following steps:
1. preparation of bismaleimide resin containing Cardo ring Structure:
(1) mixing diamine, triethylamine and methyl isoamyl ketone, stirring and heating to 60-85 ℃, adding sodium acetate and dianhydride at 60-85 ℃, stirring for 6-12 h, cooling to room temperature after the reaction is finished to obtain solution A, dissolving maleic anhydride in methyl isoamyl ketone to obtain maleic anhydride solution, adding maleic anhydride solution into the solution A in portions, stirring for 2-4 h at normal temperature, and then heating to 70 DEG C ～ 80 ℃ at 70 DEG C ～ Reflux stirring for 1-4 h at 80 ℃, and cooling to room temperature after the reaction is finished to obtain a solution B;
the mol ratio of diamine to triethylamine is 1 (0.05-0.15); the mass ratio of the diamine to the sodium acetate is 1mol (0.05-0.2) g; the mol ratio of diamine to dianhydride is 1 (1.8-2.9); the mol ratio of diamine to maleic anhydride is 1 (1.5-2.5);
the structural formula of the diamine is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain bismaleimide resin containing a Cardo ring structure;
2. weighing and mixing:
weighing 100 parts of epoxy resin, 5-20 parts of bismaleimide resin containing a Cardo ring structure, 10-100 parts of curing agent, 0.1-0.5 part of initiator, 100-800 parts of inorganic filler and 0-15 parts of solvent according to parts by weight, firstly stirring the epoxy resin and the bismaleimide resin containing the Cardo ring structure for 5-60 minutes at the temperature of 70-80 ℃, cooling, adding the solvent, dispersing for 2-10 minutes at the rotation speed of 500-2000 rpm, then adding the curing agent, the initiator and the inorganic filler, dispersing for 2-10 minutes at the rotation speed of 500-2000 rpm, and finally performing vacuum defoamation and filling to obtain the adhesive with high temperature, high adhesion strength and low viscosity.
The beneficial effects of the invention are as follows: the bismaleimide resin containing the Cardo ring structure prepared by the invention. Firstly, the molecular structure of the adhesive contains an aromatic heterocyclic structure, has excellent thermo-mechanical property, and can enhance the bonding strength of the whole system at high temperature. And secondly, the structure of the resin contains a flexible siloxane chain segment, so that the resin has lower viscosity compared with bismaleimide resin with a pure aromatic heterocyclic structure, and meanwhile, the bonding strength of a cured product to materials such as metal, silicon, glass and the like is also improved. In addition, the non-coplanar structure of the Cardo ring structure greatly reduces the symmetry and regularity of the molecular structure, reduces the crystallinity, reduces the viscosity of the resin to a certain extent, and enhances the solubility of the resin.
According to the invention, the epoxy resin system is adopted as a main structure of the electronic adhesive, and the Cardo-ring structure bismaleimide resin is adopted as a modifier, so that compared with the electronic adhesive of a pure epoxy resin system or a pure aromatic heterocyclic structure bismaleimide resin modified epoxy resin system, the thermal mechanical property of the material, especially the bonding strength at high temperature, is improved, and meanwhile, the lower viscosity of the whole system is maintained, so that the epoxy adhesive can be applied to high-speed dispensing and glue spraying processes. In addition, after the bismaleimide resin is mixed with a specific type of epoxy resin, the wettability of the bismaleimide resin to the surface of silver powder is unexpectedly improved due to the irregular entanglement phenomenon of a molecular chain segment, so that the overall dispersibility of the material is enhanced, and the viscosity is reduced to a certain extent, which is difficult to realize by other types of modifiers (such as bismaleimide with a wholly aromatic structure, acrylic resin, reactive diluent, liquid rubber and the like).
The bismaleimide resin containing the Cardo ring structure prepared by the invention can control the molecular weight and the main chain structure of the polymer by adjusting the types, the feeding proportion and the preparation process of diamine/dianhydride, so as to change the balance between the adhesiveness and the viscosity of the electronic adhesive.
The bismaleimide resin modified electronic adhesive prepared by the invention has the following advantages:
(1) The adhesive has higher bonding strength, particularly maintains certain strength at high temperature, and the chip clipper strength at 175 ℃ is more than or equal to 3.8MPa;
(2) Has higher storage modulus, can maintain certain storage modulus at high temperature, storage modulus at 175 ℃ is more than 180MPa;
(3) The system has good dispersibility, the viscosity is less than or equal to 18024cps at 5rpm, and the system can be suitable for high-speed dispensing (the lower the viscosity at 5rpm is, the faster the dispensing rate is).
The invention is used for an adhesive with high temperature, high bonding strength and low viscosity and a preparation method thereof.
Drawings
FIG. 1 is a graph showing the reference spectrum of back-scattered light of the electronic adhesive prepared in example III at 25 ℃ for 0h to 24h;
FIG. 2 is a graph showing the reference spectrum of the back-scattered light of the electronic adhesive prepared in the third embodiment at 50 ℃ for 0h to 24h;
FIG. 3 is a graph showing the backscattering light reference spectrum of the electronic adhesive prepared in comparative example one at 25℃for 0h to 24h;
FIG. 4 is a graph showing the backscattering light reference spectrum of the electronic adhesive prepared in comparative example one at 50℃for 0h to 24h;
fig. 5 is an infrared spectrum of the electronic adhesive prepared in example one.
Detailed Description
The first embodiment is as follows: the adhesive with high temperature, high bonding strength and low viscosity is prepared from 100 parts of epoxy resin, 5 to 20 parts of bismaleimide resin containing a Cardo ring structure, 10 to 100 parts of curing agent, 0.1 to 0.5 part of initiator, 100 to 800 parts of inorganic filler and 0 to 15 parts of solvent according to parts by weight;
the monomer structural formula of the bismaleimide resin containing the Cardo ring structure is as follows:
said R is 1 Is that
In this embodiment, if too much bismaleimide resin is used, the curing degree of the whole system at a certain curing temperature is reduced, the bonding strength is reduced, and meanwhile, the viscosity of the whole system is too high, so that the manufacturability of quick dispensing and glue spraying cannot be realized.
The curing agent according to the present embodiment is preferably 10 to 50 parts by mass, more preferably 10 to 30 parts by mass.
The initiator according to the present embodiment is preferably 0.1 to 0.3 parts by mass.
The inorganic filler according to the present embodiment is preferably 150 to 600 parts by mass.
The solvent according to the present embodiment is preferably 4 to 12 parts by mass.
The adhesive of the embodiment is an adhesive material with a conductive function, and can be used for bonding components in semiconductor packaging. More specifically, the electronic adhesive of the embodiment can provide better adhesive property on the premise of meeting the process of quick dispensing and glue spraying, and greatly reduces the possibility of falling off of a semiconductor element when the device is subjected to conditions such as high temperature and the like.
The bismaleimide resin used in this embodiment is a bismaleimide resin containing a Cardo ring structure. The aim of the specific embodiment is to improve the thermal mechanical property of the material, especially the bonding strength at high temperature, by introducing the bismaleimide resin containing the Cardo ring structure and the aromatic heterocyclic large side group on the main chain structure, and the long-chain siloxane contained in the bismaleimide resin reduces the viscosity of the resin by utilizing the length and the flexibility of the siloxane chain segment, and simultaneously enhances the bonding strength to metal, glass and silicon surfaces at high temperature to a certain extent.
Meanwhile, after the bismaleimide resin is combined with the specific epoxy resin, good melt fluidity is brought, so that the bismaleimide resin can be coated on the surface of the silver powder more uniformly, the agglomeration phenomenon of the specific silver powder in the electronic adhesive is unexpectedly inhibited, the dispersibility of the silver powder is improved, and the whole system is enabled to obtain lower viscosity.
The Cardo ring structure of the bismaleimide resin belongs to a rigid twisted non-coplanar structure, so that the symmetry and the repetition regularity of a molecular structure are damaged, the crystallinity of the resin is greatly reduced, and the resin has lower viscosity and better solubility. In addition, the ether bond in the molecular structure is a flexible connecting bond, so that the internal rotation resistance in the molecular chain segment can be obviously reduced, and the crystallinity of the resin is also reduced to a certain extent.
Compared with the conventional bismaleimide resin, the Cardo-ring-structure bismaleimide resin in the specific embodiment can be well dissolved in a common solvent, so that the preparation of process parameters of the electronic adhesive is very facilitated, and the viscosity of the adhesive can be further reduced.
Meanwhile, the bismaleimide resin disclosed by the specific embodiment can control the molecular weight and the main chain structure of the polymer by adjusting the types of raw materials, the feeding proportion and the preparation process, so that the viscosity and the bonding strength of the electronic adhesive are balanced.
The beneficial effects of this concrete implementation are: the bismaleimide resin containing the Cardo ring structure prepared by the specific embodiment. Firstly, the molecular structure of the adhesive contains an aromatic heterocyclic structure, has excellent thermo-mechanical property, and can enhance the bonding strength of the whole system at high temperature. And secondly, the structure of the resin contains a flexible siloxane chain segment, so that the resin has lower viscosity compared with bismaleimide resin with a pure aromatic heterocyclic structure, and meanwhile, the bonding strength of a cured product to materials such as metal, silicon, glass and the like is also improved. In addition, the non-coplanar structure of the Cardo ring structure greatly reduces the symmetry and regularity of the molecular structure, reduces the crystallinity, reduces the viscosity of the resin to a certain extent, and enhances the solubility of the resin.
In the specific embodiment, the epoxy resin system is adopted as a main structure of the electronic adhesive, and the Cardo-ring structure bismaleimide resin is adopted as a modifier, so that compared with the electronic adhesive of a pure epoxy resin system or a pure aromatic heterocyclic structure bismaleimide resin modified epoxy resin system, the thermal mechanical property of the material, especially the bonding strength at high temperature, is improved, and meanwhile, the lower viscosity of the whole system is maintained, so that the electronic adhesive can be applied to high-speed dispensing and glue spraying processes. In addition, after the bismaleimide resin is mixed with the specific type of epoxy resin, the wettability of the bismaleimide resin to the surface of silver powder is unexpectedly improved due to the irregular entanglement phenomenon of a molecular chain segment, so that the dispersibility of the whole material is enhanced, and the viscosity is reduced to a certain extent, which is difficult to realize by other types of modifiers (such as bismaleimide with a wholly aromatic structure, acrylic resin, reactive diluent, liquid rubber and the like).
The bismaleimide resin containing the Cardo ring structure prepared by the specific embodiment changes the balance between the adhesiveness and the viscosity of the electronic adhesive by controlling the molecular weight and the main chain structure of the polymer through adjusting the type, the feeding proportion and the preparation process of diamine/dianhydride.
The bismaleimide resin modified electronic adhesive prepared by adopting the specific embodiment has the following advantages:
(1) The adhesive has higher bonding strength, particularly maintains certain strength at high temperature, and the chip clipper strength at 175 ℃ is more than or equal to 3.8MPa;
(2) Has higher storage modulus, can maintain certain storage modulus at high temperature, storage modulus at 175 ℃ is more than 180MPa;
(3) The system has good dispersibility, the viscosity is less than or equal to 18024cps at 5rpm, and the system can be suitable for high-speed dispensing (the lower the viscosity at 5rpm is, the faster the dispensing rate is).
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the epoxy resin molecule has more than two glycidyl groups, and the softening point is-25-100 ℃. The other is the same as in the first embodiment.
The softening point of the epoxy resin in the specific embodiment is preferably-10-20 ℃; in the case of the epoxy resin mixture, the softening point of the epoxy resin mixture still needs to satisfy the above range.
The epoxy resin according to the present embodiment is one or a mixture of several of bisphenol a type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, ether or polyether type epoxy resin, ester or polyester epoxy resin, urethane type epoxy resin, multifunctional type epoxy resin, alicyclic type epoxy resin, aliphatic epoxy resin, hydrogenated type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, ethylene oxide modified bisphenol a type epoxy resin, propylene oxide modified bisphenol a type epoxy resin, glycidyl modified polybutadiene resin, glycidyl modified triazine resin, silicone modified epoxy resin, aminophenol type epoxy resin, flexible epoxy resin, methacrylic acid modified epoxy resin, acrylic acid modified epoxy resin, special modified epoxy resin, dicyclopentadiene type epoxy resin, side chain hydroxyalkyl modified epoxy resin, long chain alkyl modified epoxy resin, imide modified epoxy resin, and carboxyl terminated nitrile rubber (CTBN) modified epoxy resin. From the viewpoint of adhesion, bisphenol type epoxy resins such as bisphenol a type epoxy resins and bisphenol F type epoxy resins are preferable, and bisphenol F type epoxy resins are more preferable.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the curing agent is one or a mixture of more of an amine curing agent, an anhydride curing agent and an imidazole curing agent. The other is the same as the first or second embodiment.
The curing agent in the specific embodiment is aliphatic amine, aromatic amine, dicyandiamide, dihydrazide compound, anhydride or phenolic resin. The dihydrazide compound is carboxylic dihydrazide such as adipic acid dihydrazide, dodecanedicarboxylic acid dihydrazide, isophthalic acid dihydrazide and parahydroxybenzoic acid dihydrazide; the anhydride is phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, dodecenyl succinic anhydride, reactants of maleic anhydride and polybutadiene, and copolymers of maleic anhydride and styrene.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the initiator is dibenzoyl peroxide. The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the inorganic filler is silver powder, copper powder, aluminum powder, iron powder, nickel powder, silver-plated copper powder or silicon dioxide; the silver powder is flaky or spherical. The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the average particle diameter D of the inorganic filler 50 Is 0.5-10 mu m. The other embodiments are the same as those of the first to fifth embodiments.
The inorganic filler according to this embodiment is preferably silver powder.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the boiling point of the solvent is 50-250 ℃. The other embodiments are the same as those of the first to sixth embodiments.
The solvent described in this embodiment is used to dissolve the epoxy resin and the bismaleimide resin. Mixing at room temperature to 80 ℃ for about 5min to 60min is typically chosen (until a homogeneous solution is formed).
The solvent according to this embodiment preferably has a boiling point of 70℃to 200 ℃.
The solvent in the specific embodiment is one or a mixture of more of toluene, acetone, butanone, xylene, N-dimethylformamide, N-dimethylacetamide, methyl isoamyl ketone, ethyl propionate, propylene glycol methyl ether, ethyl lactate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, cyclohexanone and cyclohexane.
Eighth embodiment: the preparation method of the adhesive with high temperature, high bonding strength and low viscosity in the embodiment comprises the following steps:
1. preparation of bismaleimide resin containing Cardo ring Structure:
(1) mixing diamine, triethylamine and methyl isoamyl ketone, stirring and heating to 60-85 ℃, adding sodium acetate and dianhydride at 60-85 ℃, stirring for 6-12 h, cooling to room temperature after the reaction is finished to obtain solution A, dissolving maleic anhydride in methyl isoamyl ketone to obtain maleic anhydride solution, adding maleic anhydride solution into the solution A in portions, stirring for 2-4 h at normal temperature, and then heating to 70 DEG C ～ 80 ℃ at 70 DEG C ～ At 80 DEG CReflux stirring for 1-4 h, and cooling to room temperature after the reaction is finished to obtain a solution B;
the mol ratio of diamine to triethylamine is 1 (0.05-0.15); the mass ratio of the diamine to the sodium acetate is 1mol (0.05-0.2) g; the mol ratio of diamine to dianhydride is 1 (1.8-2.9); the mol ratio of diamine to maleic anhydride is 1 (1.5-2.5);
the structural formula of the diamine is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain bismaleimide resin containing a Cardo ring structure;
2. weighing and mixing:
weighing 100 parts of epoxy resin, 5-20 parts of bismaleimide resin containing a Cardo ring structure, 10-100 parts of curing agent, 0.1-0.5 part of initiator, 100-800 parts of inorganic filler and 0-15 parts of solvent according to parts by weight, firstly stirring the epoxy resin and the bismaleimide resin containing the Cardo ring structure for 5-60 minutes at the temperature of 70-80 ℃, cooling, adding the solvent, dispersing for 2-10 minutes at the rotation speed of 500-2000 rpm, then adding the curing agent, the initiator and the inorganic filler, dispersing for 2-10 minutes at the rotation speed of 500-2000 rpm, and finally performing vacuum defoamation and filling to obtain the adhesive with high temperature, high adhesion strength and low viscosity.
The adhesive according to the present embodiment is mixed using a disperser, a kneader, a three-roll, or the like, preferably using a disperser, and more preferably a planetary disperser.
The present embodiment preferably disperses for 4min to 6min under the condition that the rotation speed is 800rpm to 1800rpm
Detailed description nine: this embodiment differs from the eighth embodiment in that: the volume ratio of the mol of diamine to methyl isoamyl ketone in the step one (1) is 1mol (2 to 4.5) L; the volume ratio of the mol of the maleic anhydride to the methyl isoamyl ketone in the step one (1) is 1mol (0.5 to 2) L. The other is the same as in embodiment eight.
Detailed description ten: this embodiment differs from one of the eighth or ninth embodiments in that: washing and drying in the step (2) specifically comprises the steps of washing with 10-20% of sodium bicarbonate solution by mass percent, washing with deionized water as a washing liquid until the washing liquid is neutral, and finally vacuum drying for 10h at the temperature of 40-60 ℃. The others are the same as those of the eighth or ninth embodiment.
The following examples are used to verify the benefits of the present invention:
embodiment one:
the preparation method of the adhesive with high temperature, high bonding strength and low viscosity comprises the following steps:
1. preparation of bismaleimide resin containing Cardo ring Structure:
(1) mixing 1.1mol of diamine, 0.1mol of triethylamine and 3L of methyl isoamyl ketone, stirring and heating to 85 ℃, adding 0.15g of sodium acetate and 2.45mol of dianhydride at the temperature of 85 ℃, stirring for 8 hours, cooling to room temperature after the reaction is finished to obtain a solution A, dissolving 1L of maleic anhydride in the methyl isoamyl ketone to obtain a maleic anhydride solution, adding the maleic anhydride solution into the solution A in a divided manner, stirring for 2 hours at the room temperature, heating to 80 ℃, refluxing and stirring for 3 hours at the temperature of 80 ℃, and cooling to the room temperature after the reaction is finished to obtain a solution B;
the structural formula of the diamine is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain bismaleimide resin containing a Cardo ring structure;
the monomer structural formula of the bismaleimide resin containing the Cardo ring structure is as follows:
2. weighing and mixing:
weighing 100 parts of bisphenol F epoxy resin, 15 parts of bismaleimide resin containing a Cardo ring structure, 20 parts of dicyandiamide, 0.3 part of dibenzoyl peroxide and 400 parts of spherical silver powder according to parts by weight, stirring the bisphenol F epoxy resin and the bismaleimide resin containing the Cardo ring structure for 15 minutes at the temperature of 80 ℃, cooling, adding the dicyandiamide, the dibenzoyl peroxide and the spherical silver powder, dispersing for 10 minutes in a planetary dispersing machine at the rotating speed of 1500rpm, and finally carrying out vacuum defoaming and filling to obtain the electronic adhesive;
the average particle diameter D of the spherical silver powder 50 4.4 μm and a specific surface area of 1.01m 2 /g。
The washing and drying in the step (2) is specifically to wash with 10% sodium bicarbonate solution by mass percent, then wash with deionized water as a washing liquid until the washing liquid is neutral, and finally dry for 10 hours in vacuum under the condition of 60 ℃.
Embodiment two: the first difference between this embodiment and the first embodiment is that: preparing bismaleimide resin containing Cardo ring structure in the first step:
(1) mixing 0.9mol of diamine, 0.1mol of triethylamine and 3.5L of methyl isoamyl ketone, stirring and heating to 85 ℃, adding 0.12g of sodium acetate and 2.2mol of dianhydride at the temperature of 85 ℃, stirring for 6 hours, cooling to room temperature after the reaction is finished to obtain a solution A, dissolving 1L of maleic anhydride in the methyl isoamyl ketone to obtain a maleic anhydride solution, adding the maleic anhydride solution into the solution A in a divided manner, stirring for 4 hours at normal temperature, then heating to 70 ℃, refluxing and stirring for 2 hours at the temperature of 70 ℃, and cooling to room temperature after the reaction is finished to obtain a solution B;
the structural formula of the diamine is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain bismaleimide resin containing a Cardo ring structure;
the monomer structural formula of the bismaleimide resin containing the Cardo ring structure is as follows:
the other is the same as in the first embodiment.
Embodiment III: the first difference between this embodiment and the first embodiment is that: preparing bismaleimide resin containing Cardo ring structure in the first step:
(1) mixing 1.3mol of diamine, 0.1mol of triethylamine and 3.5L of methyl isoamyl ketone, stirring and heating to 85 ℃, adding 0.1g of sodium acetate and 2.9mol of dianhydride at the temperature of 85 ℃, stirring for 6 hours, cooling to room temperature after the reaction is finished to obtain a solution A, dissolving 1L of maleic anhydride in the methyl isoamyl ketone to obtain a maleic anhydride solution, adding the maleic anhydride solution into the solution A in a divided manner, stirring for 4 hours at the room temperature, then heating to 75 ℃, refluxing and stirring for 3 hours at the temperature of 75 ℃, and cooling to the room temperature after the reaction is finished to obtain a solution B;
the structural formula of the diamine is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain bismaleimide resin containing a Cardo ring structure;
the monomer structural formula of the bismaleimide resin containing the Cardo ring structure is as follows:
. The other is the same as in the first embodiment.
Embodiment four: the present embodiment is different from the third embodiment in that: average particle diameter D of spherical silver powder described in step two 50 4.9 μm and a specific surface area of 1.19m 2 And/g. The other is the same as the embodiment.
Fifth embodiment: the present embodiment is different from the third embodiment in that: average particle diameter D of spherical silver powder described in step two 50 5.8 μm, and a specific surface area of 0.56m 2 And/g. The other is the same as the embodiment.
Example six: the present embodiment is different from the third embodiment in that: average particle diameter D of spherical silver powder described in step two 50 At a ratio of 3.4 μmSurface area of 0.45m 2 And/g. The other is the same as the embodiment.
Embodiment seven: the present embodiment is different from the third embodiment in that: average particle diameter D of spherical silver powder described in step two 50 1.5 μm and a specific surface area of 0.9m 2 And/g. The other is the same as the embodiment.
Example eight: the present embodiment is different from the third embodiment in that: in the second step, 100 parts of bisphenol F type epoxy resin, 15 parts of bismaleimide resin containing a Cardo ring structure, 20 parts of dicyandiamide, 0.3 part of dibenzoyl peroxide, 400 parts of spherical silver powder and 8 parts of butanone are weighed according to the parts by weight, firstly, the bisphenol F type epoxy resin and the bismaleimide resin containing the Cardo ring structure are stirred for 15min at the temperature of 80 ℃, after cooling, the butanone is added, the dispersion is carried out for 5min at the rotating speed of 800rpm, then the dicyandiamide, the dibenzoyl peroxide and the spherical silver powder are added, then the dispersion is carried out for 10min in a planetary dispersing machine at the rotating speed of 1500rpm, and finally the electronic adhesive is obtained after vacuum defoamation and filling. The other is the same as the embodiment.
Example nine: the first difference between this embodiment and the first embodiment is that: the 100 parts of bisphenol F type epoxy resin described in the second step is replaced with 100 parts of bisphenol A type epoxy resin. The other is the same as in the first embodiment.
Comparative example one: the first difference between this comparative example and the example is: in the second step, 15 parts of bismaleimide resin containing a Cardo ring structure is replaced with 15 parts of N, N '-4,4' -diphenylmethane bismaleimide resin. The other is the same as in the first embodiment.
Comparative example two: the first difference between this comparative example and the example is: in the second step, 15 parts of bismaleimide resin containing a Cardo ring structure is replaced by 15 parts of N, N '-4,4' -diphenylmethane bismaleimide resin; average particle diameter D of spherical silver powder described in step two 50 4.9 μm and a specific surface area of 1.19m 2 And/g. The other is the same as in the first embodiment.
Comparative example three: the first difference between this comparative example and the example is: in the second step, 15 parts of bismaleimide resin containing Cardo ring structure is replaced by 15 parts of N, N '-4,4' -diphenylmethane bismaleimide resinAn imide resin; average particle diameter D of spherical silver powder described in step two 50 5.8 μm, and a specific surface area of 0.56m 2 And/g. The other is the same as in the first embodiment.
Comparative example four: the first difference between this comparative example and the example is: in the second step, 15 parts of bismaleimide resin containing a Cardo ring structure is replaced by 15 parts of N, N '-4,4' -diphenylmethane bismaleimide resin; average particle diameter D of spherical silver powder described in step two 50 3.4 μm and a specific surface area of 0.45m 2 And/g. The other is the same as in the first embodiment.
Comparative example five: the first difference between this comparative example and the example is: in the second step, 15 parts of bismaleimide resin containing a Cardo ring structure is replaced by 15 parts of N, N '-4,4' -diphenylmethane bismaleimide resin; average particle diameter D of spherical silver powder described in step two 50 1.5 μm and a specific surface area of 0.9m 2 And/g. The other is the same as in the first embodiment.
Comparative example six: this comparative example differs from example eight in that: in the second step, 15 parts of bismaleimide resin containing a Cardo ring structure is replaced with 15 parts of N, N '-4,4' -diphenylmethane bismaleimide resin. The other is the same as in the eighth embodiment.
Comparative example seven: the first difference between this comparative example and the example is: the 100 parts of bisphenol F type epoxy resin is replaced by 100 parts of bisphenol A type epoxy resin; in the second step, 15 parts of bismaleimide resin containing a Cardo ring structure is replaced with 15 parts of N, N '-4,4' -diphenylmethane bismaleimide resin. The other is the same as in the first embodiment.
Comparative example eight: the first difference between this comparative example and the example is: in the second step, 15 parts of bismaleimide resin containing the Cardo ring structure is replaced by 15 parts of o-cresol type phenolic epoxy resin. The other is the same as in the first embodiment.
Comparative example nine: the first difference between this comparative example and the example is: in the second step, 15 parts of bismaleimide resin containing the Cardo ring structure is replaced by 15 parts of liquid nitrile rubber. The other is the same as in the first embodiment.
Comparative example ten: the first difference between this comparative example and the example is: in the second step, 15 parts of bismaleimide resin containing a Cardo ring structure was replaced with 15 parts of polypropylene glycol diglycidyl ether. The other is the same as in the first embodiment.
Comparative example eleven: the first difference between this comparative example and the example is: in the second step, 115 parts of bisphenol F type epoxy resin, 20 parts of dicyandiamide and 400 parts of spherical silver powder are weighed according to the parts by weight, the epoxy resin, the dicyandiamide and the spherical silver powder are dispersed in a planetary dispersing machine for 10min under the condition that the rotating speed is 1500rpm, and finally the vacuum defoamation and the filling are carried out for later use. The other is the same as in the first embodiment.
The conductive adhesives prepared in examples one to nine and comparative examples one to eleven were tested for viscosity, chip shear strength, tensile shear strength, storage modulus, thermal weight loss, glue uniformity, stability and solubility, and the detailed evaluation methods were as follows:
1. viscosity: the uncured samples were viscosity tested using a Bowler-femto DV3T cone-plate viscometer at 25 ℃ + -1℃with rotational speeds of 0.5rpm and 5rpm respectively.
2. Chip clipper strength: bonding a 2mm multiplied by 2mm silicon wafer on a silicon substrate by using an electronic adhesive, and curing the following conditions: the sample was subjected to compression shear test using a chip push-pull force tester (Nordsondage 3800) at a shear rate of 100 μm/s by heating at 150℃for 30min and then at 200℃for 30min. The test temperatures were 25℃and 100℃and 150℃and 175℃respectively.
3. Tensile shear strength: the tensile shear test is carried out on the sample by using a universal mechanical experiment machine, the test piece is made of glass, and the bonding area is 300mm 2 Curing conditions: heating at 150deg.C for 30min, and heating at 200deg.C for 30min. The test temperature was 25℃and 100℃and 150℃and 175℃respectively, and the shear rate was 10mm/min.
4. Storage modulus: the cured samples were tested using a dynamic thermo-mechanical analyzer (DMA). Rate of temperature rise: 5 ℃/min. The test temperature is 25 ℃, 100 ℃, 150 ℃ and 175 ℃ respectively; curing conditions: heating at 150deg.C for 30min, and heating at 200deg.C for 30min.
5. Weight loss on heat: the cured samples were tested using a Thermal Gravimetric Analyzer (TGA). Rate of temperature rise: 10 ℃/min; test atmosphere: air. The curing process comprises the following steps: heating at 150deg.C for 30min, and heating at 200deg.C for 30min.
6. The electronic adhesives prepared in the third, fourth, fifth, sixth and ninth examples and the first, second, third, fourth and seventh comparative examples were subjected to glue uniformity and stability test, and the detailed evaluation method is as follows:
the uncured samples were tested using a multiplex light scattering (AGS). Sample cell volume: 20mL; the measuring probe measures every 40 mu m from the bottom of the sample cell to the top of the sample cell, and the measurement of the sample cell from bottom to top is called one scanning, and the scanning is performed once per hour for 24 hours; the test temperature is respectively 25 ℃ and 50 ℃; during data analysis, the data in the middle part of the sample pool are sampled. The back-scattered light variation value in the middle part of the sample cell refers to the back-scattered light variation value with the height of 5-18 mm.
7. Solubility: the solubility of the Cardo ring structure-containing bismaleimide resins prepared in examples one to three was measured in terms of whether 55g was dissolved in 100g of the solvent and whether or not the resin was precipitated at room temperature within 240 hours was the criterion for judging the solubility.
TABLE 1
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TABLE 4 Table 4
TABLE 5
TABLE 6
FIG. 1 is a graph showing a reference back-scattered light spectrum of the electronic adhesive prepared in the third embodiment at 25 ℃ for 0-24 hours, wherein the back-scattered light intensity variation range is extremely small within the height range of 2-22 mm, which indicates that the particle size of particles in a sample is relatively stable and no obvious agglomeration phenomenon occurs.
FIG. 2 is a graph showing a reference back-scattered light spectrum of the electronic adhesive prepared in example III at 50 ℃ for 0-24 hours, wherein the back-scattered light intensity variation range is smaller in the height range of 2-24 mm, and small fluctuation occurs at several positions, which indicates that the particle size of a small part of particles in a sample is increased, and a small amount of agglomeration phenomenon occurs.
FIG. 3 is a graph showing a reference back-scattered light spectrum of the electronic adhesive prepared in the first comparative example at 25 ℃ for 0-24 hours, wherein the back-scattered light intensity variation range is smaller in the height range of 2-30 mm, and small-amplitude fluctuation occurs at a plurality of positions, which indicates that the particle size of a very small part of particles in a sample is increased, and a very small amount of agglomeration phenomenon occurs.
FIG. 4 is a graph showing a reference back-scattered light spectrum of the electronic adhesive prepared in the first comparative example at 50 ℃ for 0-24 hours, wherein the back-scattered light intensity has a larger variation range within the height range of 2-18 mm, and the whole electronic adhesive fluctuates, which indicates that the particle size of most particles in a sample is increased to different degrees and a large amount of agglomeration phenomenon occurs.
FIG. 5 is an infrared spectrum of the electronic adhesive prepared in example one; as can be seen from the figure, 1703cm -1 Near the imide ring, a carbonyl stretching vibration absorption peak appears, 1363cm -1 、1172cm -1 C-N-C asymmetric and symmetric telescopic vibration absorption peak appears nearby, 3460cm -1 The nearby weak peak is the generalized frequency peak of carbonyl, and 1260cm -1 、816cm -1 A silane characteristic peak appears nearby. The appearance of these characteristic peaks indicates the synthesis of bismaleimide monomers.
Examples one to seven compare to comparative examples one to five:
compared with the bismaleimide resin with a full aromatic ring structure, the bismaleimide resin containing the Cardo ring structure in the embodiment 1 can generally bring lower viscosity and higher room-temperature adhesive strength to the system.
2. For particle size D 50 Silver powder with the thickness of about 4-5 mu m can be coated on the surface of the silver powder more uniformly after the bismaleimide resin and the bisphenol F type epoxy resin are combined, so that the overall viscosity is reduced more remarkably, and meanwhile, the overall dispersibility and stability of the glue solution are better.
Examples one to nine compare to comparative examples eight to eleven:
compared with high-temperature-resistant epoxy resin, rubber toughening and reactive diluents, the bismaleimide resin disclosed by the embodiment can bring higher high-temperature bonding strength, lower thermal weight loss rate and higher storage modulus at high temperature to a system.
Example eight compared to comparative example six:
the examples have lower viscosity, indicating that the bismaleimide resin containing Cardo ring structure has better solubility in butanone than the bismaleimide resin containing full aromatic ring structure.
Examples one to nine are all useful as high temperature high strength low viscosity electronic adhesives.
Claims (3)
1. The adhesive with high temperature, high bonding strength and low viscosity is characterized by being prepared from 100 parts of epoxy resin, 15 parts of bismaleimide resin containing a Cardo ring structure, 20 parts of curing agent, 0.3 part of initiator and 400 parts of inorganic filler according to parts by weight; the epoxy resin is bisphenol F type epoxy resin; the inorganic filler is spherical silver powder, and the average particle diameter D of the spherical silver powder 50 4.4 μm and a specific surface area of 1.01m 2 Average particle diameter D of/g, or spherical silver powder 50 4.9 μm and a specific surface area of 1.19m 2 /g；
The bismaleimide resin with the Cardo ring structure is prepared by the following steps:
(1) mixing diamine, triethylamine and methyl isoamyl ketone, stirring and heating to 60-85 ℃, adding sodium acetate and dianhydride at 60-85 ℃, stirring for 6-12 h, cooling to room temperature after the reaction is finished to obtain solution A, dissolving maleic anhydride in methyl isoamyl ketone to obtain maleic anhydride solution, adding maleic anhydride solution into the solution A in portions, stirring for 2-4 h at normal temperature, and then heating to 70 DEG C ～ 80 ℃ at 70 DEG C ～ Reflux stirring for 1-4 h at 80 ℃, and cooling to room temperature after the reaction is finished to obtain a solution B;
the mol ratio of diamine to triethylamine is 1 (0.05-0.15); the mass ratio of the diamine to the sodium acetate is 1mol (0.05-0.2) g; the mol ratio of diamine to dianhydride is 1 (1.8-2.9); the mol ratio of diamine to maleic anhydride is 1 (1.5-2.5);
the structural formula of the diamine is
The structural formula of the dibasic anhydride is
(2) Adding deionized water into the solution B, precipitating and separating out a product, filtering, washing and drying to obtain the bismaleimide resin containing the Cardo ring structure.
2. The adhesive with high temperature, high bonding strength and low viscosity according to claim 1, wherein the curing agent is one or a mixture of more of an amine curing agent, an acid anhydride curing agent and an imidazole curing agent.
3. The adhesive of claim 1 wherein said initiator is dibenzoyl peroxide.
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| JP2001261939A (en) * | 2000-03-21 | 2001-09-26 | Sumitomo Bakelite Co Ltd | Liquid resin composition and semiconductor device by using the same |
| CN101007778A (en) * | 2007-01-10 | 2007-08-01 | 复旦大学 | Chain-prolonged type fluorenyl bimaleimide and its preparation method |
| CN102604043A (en) * | 2012-02-29 | 2012-07-25 | 株洲时代新材料科技股份有限公司 | Double-component imine modified epoxy solvent-free impregnated resin and preparation and use methods |
| CN105153009A (en) * | 2015-06-23 | 2015-12-16 | 复旦大学 | Bimaleimide with asymmetric molecular structure and preparation methods thereof, and application of bimaleimide in preparation of composite resin |
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| US8637611B2 (en) * | 2008-08-13 | 2014-01-28 | Designer Molecules, Inc. | Amide-extended crosslinking compounds and methods for use thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001261939A (en) * | 2000-03-21 | 2001-09-26 | Sumitomo Bakelite Co Ltd | Liquid resin composition and semiconductor device by using the same |
| CN101007778A (en) * | 2007-01-10 | 2007-08-01 | 复旦大学 | Chain-prolonged type fluorenyl bimaleimide and its preparation method |
| CN102604043A (en) * | 2012-02-29 | 2012-07-25 | 株洲时代新材料科技股份有限公司 | Double-component imine modified epoxy solvent-free impregnated resin and preparation and use methods |
| CN105153009A (en) * | 2015-06-23 | 2015-12-16 | 复旦大学 | Bimaleimide with asymmetric molecular structure and preparation methods thereof, and application of bimaleimide in preparation of composite resin |
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