CN111394053B - Non-flowing underfill with welding assisting function and preparation method thereof - Google Patents

Non-flowing underfill with welding assisting function and preparation method thereof Download PDF

Info

Publication number
CN111394053B
CN111394053B CN202010139004.3A CN202010139004A CN111394053B CN 111394053 B CN111394053 B CN 111394053B CN 202010139004 A CN202010139004 A CN 202010139004A CN 111394053 B CN111394053 B CN 111394053B
Authority
CN
China
Prior art keywords
acid
accounts
underfill
adhesive system
filled adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN202010139004.3A
Other languages
Chinese (zh)
Other versions
CN111394053A (en
Inventor
潘朝群
祝立强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN202010139004.3A priority Critical patent/CN111394053B/en
Publication of CN111394053A publication Critical patent/CN111394053A/en
Application granted granted Critical
Publication of CN111394053B publication Critical patent/CN111394053B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Epoxy Resins (AREA)
  • Wire Bonding (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

The invention belongs to the technical field of flip chip underfill processes, and particularly relates to a non-flowing underfill with a soldering assistant function and a preparation method thereof. The preparation method comprises the following steps of (1) taking 1,3,5, 7-tetramethylcyclotetrasiloxane, 4-vinyl epoxy cyclohexane, 1-dodecene and a platinum catalyst as raw materials, and carrying out hydrosilylation reaction under the heating and stirring conditions to prepare epoxy modified silicone resin; (2) and (2) preparing the non-flowing underfill with the soldering-assistant function by matching the epoxy modified silicone resin prepared in the step (1) with a curing agent, an activating agent, a solvent and other auxiliaries. The underfill prepared by the invention can realize solder ball welding while being cured in the reflow soldering process, thereby saving the steps of distributing and removing soldering flux in the traditional flip chip underfill process and greatly improving the production efficiency. And the epoxy modified silicone resin has the advantages of organic silicon and epoxy, has excellent heat resistance and flexibility after being cured, has a lower thermal expansion coefficient, and better meets the packaging requirements of flip chips.

Description

Non-flowing underfill with welding assisting function and preparation method thereof
Technical Field
The invention belongs to the technical field of flip chip underfill processes, and particularly relates to a non-flowing underfill with a soldering assistant function and a preparation method thereof.
Background
Flip chip packaging technology has attracted much attention in electronic packaging due to its high number of I/os per unit area, short signal path, high heat dissipation, and good electrical and thermodynamic properties. The flip chip packaging technology is characterized in that a bare chip is directly connected to a substrate through a solder ball, and underfill is filled in a gap between the chip and the substrate to reduce stress generated by mismatch of thermal expansion coefficients of the chip and the substrate and improve packaging stability.
In the traditional underfill process, a layer of soldering flux is coated on a substrate, then solder bumps are aligned with pads of the substrate, heating and refluxing are carried out, the soldering flux is removed, underfill is injected along the edge of a chip, the underfill is sucked and flows to the center of the substrate of the chip by virtue of the capillary action of liquid, and heating and curing are carried out after the underfill is filled. Wherein if the flux is not cleaned, ionic residue can be formed, thereby reducing the reliability of product equipment. Moreover, the underfill fills the gap between the chip and the substrate by capillary action, which may leave a gap in the central area of the gap, thereby causing packaging hidden troubles. With the miniaturization of electrical components, the restriction of capillary action is increasing.
The non-flowing underfill is coated on the substrate, then the solder bumps are aligned to the substrate pads, and then the solder ball welding and the underfill solidification are simultaneously completed in the reflow soldering process, so that the soldering flux distribution and cleaning steps in the traditional flip chip underfill process are omitted, and the production efficiency is greatly improved.
At present, a great deal of documents are prepared from epoxy resin by curing and film-forming, and for example, chinese patent CN 102554512 a discloses a curable flux composition and a soldering method, which are prepared by mixing epoxy resin, a curing agent, an activator and an auxiliary agent. Although the epoxy resin has excellent adhesiveness, the epoxy resin has the problems of large internal stress, large thermal expansion coefficient, low glass transition temperature and easy bubbling and cracking of a cured film at a reflow soldering temperature. The epoxy modified silicone resin has the advantages of both organic silicon and epoxy, and has excellent heat resistance, flexibility and spreadability and a lower thermal expansion coefficient. Therefore, the non-flowing underfill prepared from the epoxidized modified silicone resin fundamentally meets the packaging requirements of the flip chip.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention is primarily directed to a method for preparing a no-flow underfill with a fluxing function.
Another object of the present invention is to provide a non-flowing underfill with a fluxing function obtained by the above preparation method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of non-flowing underfill with a welding-assistant function comprises the following steps:
(1) preparation of epoxidized modified Silicone resins
Heating and stirring 1,3,5, 7-tetramethylcyclotetrasiloxane, 4-vinyl cyclohexene oxide, 1-dodecene and a platinum catalyst serving as raw materials at 90-130 ℃ for 2-4 h to perform hydrosilylation reaction to prepare the epoxidized modified silicone resin;
in the raw materials, the molar ratio of a silicon-hydrogen bond to vinyl is 1:1.2, the molar ratio of 4-vinyl epoxy cyclohexane to 1-dodecene is 1: 1-3: 1, and the dosage of a platinum catalyst is 3-8 ppm;
(2) preparation of the Filler gels
Uniformly mixing the epoxidized modified silicone resin prepared in the step (1), a curing agent, an activating agent, a solvent and other auxiliaries to obtain the non-flowing underfill with the soldering-assisting function;
the curing agent is acid anhydride;
the activating agent is organic carboxylic acid with more than two functions;
the solvent is alcohol;
the other auxiliary agents comprise one or more than two of a surfactant, a coupling agent and a latent curing agent;
The dosage of the epoxidized modified silicone resin accounts for 40-60% of the filled adhesive system;
the amount of the curing agent accounts for 10-20% of the filled adhesive system;
the dosage of the activating agent accounts for 10-20% of the filled adhesive system;
the dosage of the solvent accounts for 20-40% of the filled adhesive system;
the dosage of the other preparation accounts for 1 to 5 percent of the filling adhesive system;
the amounts of the epoxidized modified silicone resin, curing agent, activator, solvent and other auxiliaries are 100% in total.
Preferably, the dosage of the epoxidized modified silicone resin accounts for 40-52% of the filled adhesive system; the amount of the curing agent accounts for 10-16% of the filled adhesive system; the dosage of the activating agent accounts for 12-17% of the filled adhesive system; the dosage of the solvent accounts for 20-30% of the filled adhesive system; the dosage of the other preparation accounts for 2 to 3.8 percent of the filling adhesive system.
Preferably, the hydrosilylation reaction is carried out for 3-4 hours at 100-120 ℃.
Preferably, the acid anhydride described in step (2) includes one or more of an alicyclic acid anhydride, an aliphatic acid anhydride, and an aromatic acid anhydride.
More preferably, the alicyclic acid anhydride in the step (2) includes methyl hexahydrophthalic anhydride and/or methyl tetrahydrophthalic anhydride; the aliphatic anhydride comprises dodecenyl succinic anhydride and/or dodecenyl succinic anhydride; the aromatic acid anhydride comprises phthalic anhydride and/or trimellitic anhydride.
Among the above curing agents, alicyclic acid anhydrides are preferably used, and methylhexahydrophthalic anhydride is more preferred, from the viewpoints of high-temperature stability and resin airtightness after curing.
Preferably, the organic carboxylic acid having two or more functional groups in step (2) includes one or more of a saturated aliphatic dicarboxylic acid, an unsaturated aliphatic dicarboxylic acid, a cyclic aliphatic carboxylic acid, a saturated aliphatic dicarboxylic acid having a side chain, and a hydroxyl group-containing carboxylic acid.
More preferably, the saturated aliphatic dicarboxylic acid in step (2) comprises one or more of oxalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid and dodecanedioic acid; the unsaturated aliphatic dicarboxylic acid is itaconic acid and/or mesaconic acid; the cyclic aliphatic carboxylic acid comprises one or more than two of cyclic succinic acid, cyclohexanedicarboxylic acid and cyclopentanetetracarboxylic acid; the saturated aliphatic dicarboxylic acid with the side chain is dimethyl glutaric acid and/or methyl adipic acid; the hydroxyl-containing carboxylic acid is one or more than two of citric acid, malic acid and tartaric acid.
From the viewpoint of the activity and storage stability of the organic carboxylic acid and the maintenance of the activity throughout the entire reflow temperature range, 2 or 3 kinds of oxalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, dodecanedioic acid, and the like of the saturated aliphatic dicarboxylic acid are preferably used in combination as the activator. The organic carboxylic acid can remove the oxide film on the surface of the substrate to achieve the effect of soldering aid, and can also participate in the curing of the epoxy resin.
Preferably, the alcohols in step (2) include monohydric alcohols and/or polyhydric alcohols.
More preferably, the alcohol in step (2) includes one or more of methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol and glycerol.
A mixture of a polyhydric alcohol and a monohydric alcohol is preferred, which provides a cured flux after reflow soldering with good insulation properties. The alcohols have excellent solubility, and can dissolve organic carboxylic acid so as to adjust the viscosity of the system.
Preferably, the surfactant in step (2) comprises one or more of span series, tween series, OP series and dibromobutenediol. The surfactant may improve the wettability of the underfill.
More preferably, the surfactant in the step (2) accounts for 0.5-2% of the filled adhesive system.
More preferably, the surfactant in the step (2) accounts for 0.7-1% of the filled adhesive system.
Preferably, the coupling agent in the step (2) is one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane. The coupling agent can improve the bonding force between the filling adhesive and the base material.
More preferably, the coupling agent in the step (2) accounts for 0.2-1.1% of the filled adhesive system.
Further preferably, the coupling agent in the step (2) accounts for 0.5-1.1% of the filled adhesive system.
Preferably, the latent curing agent in step (2) is a metal chelate and/or imidazole. The latent curing agent may facilitate curing of the underfill.
More preferably, the latent curing agent in the step (2) accounts for 1-3% of the filled adhesive system.
More preferably, the latent curing agent in the step (2) accounts for 1.4-2% of the filled adhesive system.
The invention further provides the non-flowing underfill with the soldering-assistant function, which is prepared by the preparation method, wherein the glass transition temperature of the underfill is 99-132 ℃, and the thermal expansion coefficient is 22-33 ppm/DEG C.
Compared with the prior art, the invention has the following beneficial effects:
(1) the non-flowing underfill with the soldering-assistant function can also finish solder ball soldering while being cured in the reflow soldering process, thereby saving the soldering flux distribution and clearing steps in the traditional flip chip underfill process and greatly improving the production efficiency. The method can be applied to flip chips with larger chip size, smaller solder ball distance and smaller chip-substrate gap, and the traditional underfill material can not flow through the capillary.
(2) The epoxy modified silicone resin has the advantages of organic silicon and epoxy, has excellent heat resistance and flexibility, higher glass transition temperature, lower thermal expansion coefficient and high reliability, meets the performance requirement of underfill, and can better protect a flip chip.
Detailed Description
The present invention is further illustrated by the following examples, but the embodiments of the present invention are not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
The embodiment provides a non-flowing underfill with a soldering assistant function and a preparation method thereof.
(1) 24.1g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 29.8g of 4-vinylcyclohexane epoxide, 40.4g of 1-dodecene and 8ppm of platinum catalyst are taken as raw materials, heated and stirred at 100 ℃ for 3 hours to prepare the epoxy modified silicon resin.
(2) And (2) taking 40g of the epoxidized modified silicon resin prepared in the step (1), 10g of methyl hexahydrophthalic anhydride, 8g of adipic acid, 8g of succinic acid, 15.1g of ethanol, 15.1g of glycerol, 1g of OP-10, 0.8g of gamma-glycidoxypropyltrimethoxysilane and 2g of cobalt acetylacetonate into a beaker, and uniformly dispersing at a high speed to prepare the non-flowing underfill with the soldering assistant function. Finally, the glass transition temperature of the underfill was measured to be 110 ℃ and the coefficient of thermal expansion was measured to be 30 ppm/DEG C.
Example 2
The embodiment provides a non-flowing underfill with a soldering assistant function and a preparation method thereof.
(1) 24.1g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 29.8g of 4-vinyl cyclohexene oxide, 40.4g of 1-dodecene and 5ppm of platinum catalyst are taken as raw materials, heated and stirred at 110 ℃ for 4 hours to prepare the epoxy modified silicon resin.
(2) And (2) putting 48g of the epoxidized modified silicone resin prepared in the step (1), 12g of methylhexahydrophthalic anhydride, 9g of adipic acid, 8g of succinic acid, 15.1g of ethanol, 5.1g of glycerol, 0.8g of OP-10, 0.5g of gamma-methacryloxypropyltrimethoxysilane and 1.5g of 2-methylimidazole into a beaker, and uniformly dispersing at a high speed to prepare the non-flowing underfill with the welding-assistant function. Finally, the glass transition temperature of the underfill was measured to be 115 ℃ and the coefficient of thermal expansion was measured to be 33 ppm/DEG C.
Example 3
The embodiment provides a non-flowing underfill with a soldering assistant function and a preparation method thereof.
(1) 24.1g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 29.8g of 4-vinyl cyclohexene oxide, 40.4g of 1-dodecene and 3ppm of platinum catalyst are taken as raw materials, heated and stirred at 120 ℃ for 4 hours to prepare the epoxy modified silicon resin.
(2) 42g of the epoxidized modified silicone resin prepared in the step (1), 11g of methyl tetrahydrophthalic anhydride, 8g of adipic acid, 8g of glutaric acid, 13.1g of isopropanol, 14.1g of ethylene glycol, 0.7g of dibromobutenediol, 1.1g of gamma-glycidoxypropyltrimethoxysilane and 2g of cobalt acetylacetonate are put into a beaker and uniformly dispersed at a high speed to prepare the non-flowing underfill with the soldering assistant function. Finally, the glass transition temperature of the underfill was measured to be 99 ℃ and the coefficient of thermal expansion was measured to be 26 ppm/DEG C.
Example 4
The embodiment provides a non-flowing underfill with a soldering assistant function and a preparation method thereof.
(1) 24.1g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 44.7g of 4-vinyl cyclohexene oxide, 20.2g of 1-dodecene and 8ppm of platinum catalyst are taken as raw materials, heated and stirred at 100 ℃ for 3 hours to prepare the epoxy modified silicon resin.
(2) 42g of the epoxidized modified silicone resin prepared in the step (1), 10g of methyl tetrahydrophthalic anhydride, 9g of adipic acid, 8g of glutaric acid, 20.2g of isopropanol, 7.8g of glycerol, 1.0g of dibromobutenediol, 0.6g of gamma-glycidoxypropyltrimethoxysilane and 1.4g of 2-phenyl-4-methylimidazole are put into a beaker and uniformly dispersed at a high speed to prepare the non-flowing underfill with the soldering-assisting function. Finally, the glass transition temperature of the underfill was measured to be 132 ℃ and the coefficient of thermal expansion was measured to be 28 ppm/DEG C.
Example 5
The embodiment provides a non-flowing underfill with a soldering assistant function and a preparation method thereof.
(1) 24.1g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 44.7g of 4-vinyl cyclohexene oxide, 20.2g of 1-dodecene and 5ppm of platinum catalyst are taken as raw materials, heated and stirred at 110 ℃ for 4 hours to prepare the epoxy modified silicon resin.
(2) 45g of the epoxidized modified silicone resin prepared in the step (1), 13g of methyl tetrahydrophthalic anhydride, 8g of adipic acid, 9g of glutaric acid, 17.3g of isopropanol, 4.2g of ethylene glycol, 0.7g of OP-4, 0.8g of gamma-methacryloxypropyl trimethoxysilane and 2.0g of 2-phenyl-4-methylimidazole are put into a beaker and uniformly dispersed at a high speed to prepare the non-flowing underfill with the welding-assistant function. Finally, the glass transition temperature of the underfill was measured to be 116 ℃ and the coefficient of thermal expansion was measured to be 22 ppm/DEG C.
Example 6
The embodiment provides a non-flowing underfill with a soldering assistant function and a preparation method thereof.
(1) 24.1g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 44.7g of 4-vinyl cyclohexene oxide, 20.2g of 1-dodecene and 3ppm of platinum catalyst are taken as raw materials, heated and stirred at 120 ℃ for 4 hours to prepare the epoxy modified silicon resin.
(2) 48g of the epoxidized modified silicone resin prepared in the step (1), 14g of methylhexahydrophthalic anhydride, 8g of adipic acid, 7g of dodecanedioic acid, 12.4g of isopropanol, 8.1g of diethylene glycol, 0.6g of OP-10, 0.5g of gamma-methacryloxypropyltrimethoxysilane and 1.4g of 2-phenyl-4-methylimidazole are taken to be put into a beaker and uniformly dispersed at a high speed to prepare the non-flowing underfill with the welding-assistant function. Finally, the glass transition temperature of the underfill was measured to be 122 ℃ and the coefficient of thermal expansion was measured to be 31 ppm/DEG C.
Comparative example 1
The glass transition temperature of the underfill was measured to be 70 ℃ and the coefficient of thermal expansion 65 ppm/deg.C compared to commercially available HS707 underfill in Hansi chemistry.
Compared with the common underfill material, the non-flowing underfill with the soldering-assistant function has the advantages of higher glass transition temperature, lower thermal expansion coefficient and the like, and can be widely applied to the flip chip packaging process.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of non-flowing underfill with a welding-assistant function is characterized by comprising the following steps:
(1) preparation of epoxidized modified Silicone resins
Heating and stirring 1,3,5, 7-tetramethylcyclotetrasiloxane, 4-vinyl cyclohexene oxide, 1-dodecene and a platinum catalyst serving as raw materials at 90-130 ℃ for 2-4 h to perform hydrosilylation reaction to prepare the epoxidized modified silicone resin;
in the raw materials, the molar ratio of a silicon-hydrogen bond to vinyl is 1:1.2, the molar ratio of 4-vinyl epoxy cyclohexane to 1-dodecene is 1: 1-3: 1, and the dosage of a platinum catalyst is 3-8 ppm;
(2) preparation of the Filler gels
Uniformly mixing the epoxidized modified silicone resin prepared in the step (1), a curing agent, an activating agent, a solvent and other auxiliaries to obtain the non-flowing underfill with the soldering-assisting function;
the curing agent is acid anhydride;
The activating agent is organic carboxylic acid with more than two functions;
the solvent is alcohol;
the other auxiliary agents comprise one or more than two of a surfactant, a coupling agent and a latent curing agent;
the dosage of the epoxidized modified silicone resin accounts for 40-60% of the filled adhesive system;
the amount of the curing agent accounts for 10-20% of the filled adhesive system;
the dosage of the activating agent accounts for 10-20% of the filled adhesive system;
the dosage of the solvent accounts for 20-40% of the filled adhesive system;
the dosage of the other auxiliary agents accounts for 1-5% of the filled adhesive system;
the amounts of the epoxidized modified silicone resin, curing agent, activator, solvent and other auxiliaries are 100% in total.
2. The method for preparing a no-flow underfill with a fluxing function according to claim 1, wherein:
the dosage of the epoxidized modified silicone resin accounts for 40-52% of the filled adhesive system;
the amount of the curing agent accounts for 10-16% of the filled adhesive system;
the dosage of the activating agent accounts for 12-17% of the filled adhesive system;
the dosage of the solvent accounts for 20-30% of the filled adhesive system;
the dosage of the other auxiliary agents accounts for 2-3.8% of the filled adhesive system.
3. The method for preparing a no-flow underfill with a fluxing function according to claim 1, wherein: the hydrosilylation reaction in the step (1) is carried out for 3-4 hours at the temperature of 100-120 ℃.
4. The method for preparing the no-flow underfill with the solder assist function according to any one of claims 1 to 3, characterized in that:
the acid anhydride in the step (2) comprises one or more than two of alicyclic acid anhydride, aliphatic acid anhydride and aromatic acid anhydride;
the organic carboxylic acid with two or more than two functions in the step (2) comprises one or more than two of saturated aliphatic dicarboxylic acid, unsaturated aliphatic dicarboxylic acid, cyclic aliphatic carboxylic acid and hydroxyl-containing carboxylic acid;
the alcohols in the step (2) comprise monohydric alcohols and/or polyhydric alcohols.
5. The method for preparing a no-flow underfill with a fluxing function according to claim 4, wherein:
the alicyclic anhydride in the step (2) comprises methyl hexahydrophthalic anhydride and/or methyl tetrahydrophthalic anhydride; the aliphatic acid anhydride comprises dodecenyl succinic anhydride; the aromatic acid anhydride comprises phthalic anhydride and/or trimellitic anhydride;
The saturated aliphatic dicarboxylic acid in the step (2) comprises one or more than two of oxalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, dodecanedioic acid, dimethyl glutaric acid and methyl adipic acid; the unsaturated aliphatic dicarboxylic acid is itaconic acid and/or mesaconic acid; the cyclic aliphatic carboxylic acid comprises one or more than two of cyclic succinic acid, cyclohexanedicarboxylic acid and cyclopentanetetracarboxylic acid; the hydroxyl-containing carboxylic acid is one or more than two of citric acid, malic acid and tartaric acid;
the alcohol in the step (2) comprises one or more than two of methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol and glycerol.
6. The method for preparing a no-flow underfill with a fluxing function according to claim 5, wherein:
the surfactant in the step (2) comprises one or more than two of span series, Tween series, OP series and dibromobutenediol;
the coupling agent in the step (2) is one or more than two of gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane;
The latent curing agent in the step (2) is metal chelate and/or imidazole.
7. The method for preparing a no-flow underfill with a fluxing function according to claim 6, wherein:
the surfactant in the step (2) accounts for 0.5-2% of the filled adhesive system;
the coupling agent in the step (2) accounts for 0.2-1.1% of the filled adhesive system;
the latent curing agent in the step (2) accounts for 1-3% of the filled adhesive system.
8. The method for preparing a no-flow underfill with a fluxing function according to claim 7, wherein:
the surfactant in the step (2) accounts for 0.7-1% of the filled adhesive system;
the coupling agent in the step (2) accounts for 0.5-1.1% of the filled adhesive system;
the latent curing agent in the step (2) accounts for 1.4-2% of the filled adhesive system.
9. The utility model provides a take and help non-flowing underfill of welding function which characterized in that: the preparation method of any one of claims 1 to 8.
10. The no-flow underfill with fluxing functionality according to claim 9, wherein: the glass transition temperature of the filling adhesive is 99-132 ℃, and the thermal expansion coefficient is 22-33 ppm/DEG C.
CN202010139004.3A 2020-03-03 2020-03-03 Non-flowing underfill with welding assisting function and preparation method thereof Expired - Fee Related CN111394053B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010139004.3A CN111394053B (en) 2020-03-03 2020-03-03 Non-flowing underfill with welding assisting function and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010139004.3A CN111394053B (en) 2020-03-03 2020-03-03 Non-flowing underfill with welding assisting function and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111394053A CN111394053A (en) 2020-07-10
CN111394053B true CN111394053B (en) 2021-10-26

Family

ID=71427103

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010139004.3A Expired - Fee Related CN111394053B (en) 2020-03-03 2020-03-03 Non-flowing underfill with welding assisting function and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111394053B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023249123A1 (en) * 2022-06-24 2023-12-28 国立大学法人 鹿児島大学 Heat-curable composition, cured article, adhesive agent, and heat-curable composition production method

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1374168A (en) * 2000-12-04 2002-10-16 富士电机株式会社 Welding flux and brazing filler metal composition for brass solder
CN1643682A (en) * 2002-01-31 2005-07-20 国家淀粉及化学投资控股公司 No-flow underfill encapsulant
CN1643023A (en) * 2002-01-31 2005-07-20 国家淀粉及化学投资控股公司 No flow underfill composition
CN1849373A (en) * 2003-08-14 2006-10-18 通用电气公司 Nano-filled composite materials with exceptionally high glass transition temperature
CN102224583A (en) * 2008-11-25 2011-10-19 洛德公司 Methods for protecting a die surface with photocurable materials
CN102731558A (en) * 2012-06-08 2012-10-17 湖北德邦化工新材料有限公司 Organosilicone oligomer and preparation method thereof, and bi-component system and application thereof
CN104479133A (en) * 2014-12-05 2015-04-01 佛山市华联有机硅有限公司 Preparation method of long-chain alkyl modified silicone oil
CN104817989A (en) * 2015-04-10 2015-08-05 深圳广恒威科技有限公司 Underfiller composition and preparation method thereof
CN105086902A (en) * 2015-09-01 2015-11-25 烟台德邦科技有限公司 Non-flowing epoxy underfill material and preparation method thereof
CN107540843A (en) * 2017-08-31 2018-01-05 华南理工大学 The function additive of side base containing chain alkyl and epoxy based polysiloxane and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6391999B1 (en) * 1998-02-06 2002-05-21 Rensselaer Polytechnic Institute Epoxy alkoxy siloxane oligomers
US6794761B2 (en) * 2001-04-26 2004-09-21 Intel Corporation No-flow underfill material
US7279223B2 (en) * 2003-12-16 2007-10-09 General Electric Company Underfill composition and packaged solid state device
JP4300418B2 (en) * 2004-04-30 2009-07-22 信越化学工業株式会社 Epoxy / silicone hybrid resin composition and light emitting semiconductor device
CN101864147B (en) * 2010-06-28 2012-12-26 深圳市库泰克电子材料技术有限公司 Underfill with low viscosity and low linear expansion coefficient

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1374168A (en) * 2000-12-04 2002-10-16 富士电机株式会社 Welding flux and brazing filler metal composition for brass solder
CN1643682A (en) * 2002-01-31 2005-07-20 国家淀粉及化学投资控股公司 No-flow underfill encapsulant
CN1643023A (en) * 2002-01-31 2005-07-20 国家淀粉及化学投资控股公司 No flow underfill composition
CN1849373A (en) * 2003-08-14 2006-10-18 通用电气公司 Nano-filled composite materials with exceptionally high glass transition temperature
CN102224583A (en) * 2008-11-25 2011-10-19 洛德公司 Methods for protecting a die surface with photocurable materials
CN102731558A (en) * 2012-06-08 2012-10-17 湖北德邦化工新材料有限公司 Organosilicone oligomer and preparation method thereof, and bi-component system and application thereof
CN104479133A (en) * 2014-12-05 2015-04-01 佛山市华联有机硅有限公司 Preparation method of long-chain alkyl modified silicone oil
CN104817989A (en) * 2015-04-10 2015-08-05 深圳广恒威科技有限公司 Underfiller composition and preparation method thereof
CN105086902A (en) * 2015-09-01 2015-11-25 烟台德邦科技有限公司 Non-flowing epoxy underfill material and preparation method thereof
CN107540843A (en) * 2017-08-31 2018-01-05 华南理工大学 The function additive of side base containing chain alkyl and epoxy based polysiloxane and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Studies on UV-Stable Silicone–Epoxy Resins;Wei Huang 等;《Journal of Applied Polymer Science》;20070615;第104卷(第6期);第3954-3959页 *
环氧基聚硅氧烷的合成及在耐刮擦聚丙烯中的应用;梅青冉;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20190515(第05期);第B014-190页 *
环氧模塑料的低应力化技术;黄英 等;《中国塑料》;19991031;第13卷(第10期);第5-10页 *

Also Published As

Publication number Publication date
CN111394053A (en) 2020-07-10

Similar Documents

Publication Publication Date Title
JP4276085B2 (en) Underfill encapsulant for wafer packaging and coating method thereof
JP2001519838A (en) Die adhesive or encapsulant of epoxysiloxane and polyepoxy resin
JP4299140B2 (en) Double cure B-stageable underfill for wafer level
US20040143062A1 (en) Thermosetting resin composition
EP1818351B1 (en) Underfill encapsulant for wafer packaging and method for its application
US20040185603A1 (en) Flip-chip system and method of making same
KR20040088569A (en) B-stageable underfill encapsulant and method for its application
KR20030028454A (en) Fluxing Underfill Compositions
JP2009096886A (en) Liquid sealing resin composition and manufacturing method of semiconductor device using it
CN111394053B (en) Non-flowing underfill with welding assisting function and preparation method thereof
US20050048700A1 (en) No-flow underfill material having low coefficient of thermal expansion and good solder ball fluxing performance
JP2004027005A (en) Sealing liquid epoxy resin composition and semiconductor device
JP2001288445A (en) Electrically connectable semiconductor adhesive
JP2009024099A (en) Liquid epoxy resin composition and semiconductor device
CN105462531B (en) Underfill and preparation method thereof and flip-chip
JP4721309B2 (en) Thermosetting resin composition and semiconductor device
JP3773022B2 (en) Flip chip type semiconductor device
JP3938502B2 (en) Liquid encapsulating resin composition, semiconductor element assembly method, and semiconductor device
JP3732148B2 (en) Semiconductor device manufacturing method and semiconductor device
WO2004039886A2 (en) Flip-chip system and method of making same
JP2006169395A (en) Underfill resin composition
JP5557158B2 (en) Flip chip connecting underfill agent and method of manufacturing semiconductor device using the same
JP6046894B2 (en) Liquid encapsulant
JP2006188573A (en) Liquid epoxy resin composition, electronic component device using the composition and method for producing the same
JP6401041B2 (en) Curable epoxy resin composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20211026

CF01 Termination of patent right due to non-payment of annual fee