CN103289621A - Thermosetting resin composition - Google Patents
Thermosetting resin composition Download PDFInfo
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- CN103289621A CN103289621A CN2013100383678A CN201310038367A CN103289621A CN 103289621 A CN103289621 A CN 103289621A CN 2013100383678 A CN2013100383678 A CN 2013100383678A CN 201310038367 A CN201310038367 A CN 201310038367A CN 103289621 A CN103289621 A CN 103289621A
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- thermosetting resin
- packaged unit
- soldered ball
- epoxy
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
Abstract
The invention provides a thermosetting resin composition for a joining method of a packaging part. The thermosetting resin composition contains epoxy resin, organic acid and thixotropic agent, wherein the epoxy resin contains dimeric-dibasic-acid type epoxy resin. The joining method of the packaging part comprises a film forming process, a resin-composition adhesion process, a loading process and a reflow soldering process.
Description
Technical field
The present invention relates to the compositions of thermosetting resin that in the method for joining of the packaged unit with soldered ball, uses.
Background technology
Be accompanied by miniaturization and the slimming of electronics, used the packaged unit (so-called BGA Package: BGA encapsulation) with soldered ball.And, for such BGA encapsulation, also require the BGA encapsulation of fine pitch, but under the situation that BGA encapsulates with installation base plate engages with fine pitch, have the such problem of weak strength of bonding part when only engaging with soldered ball.Therefore, usually by underfill (underfill) is filled into BGA encapsulates and installation base plate between and make it solidify the bonding part is strengthened.But, expend time in order to fill underfill and to be cured, therefore, existing problems aspect production cost.
On the other hand, proposed a kind ofly to contain the caking agent of solder flux and the method (reference literature 1: Japanese kokai publication hei 4-280443 communique) of packaged unit is installed at printing in installation base plate printing in advance.
But, in the method for the use caking agent that document 1 is put down in writing, also need to carry out separately the printing process of caking agent, not only expend time in, and need special equipment, therefore, existing problems aspect production cost.
Summary of the invention
Therefore, inventor waits and propose to have a kind of method of joining of packaged unit that can guarantee to have the bond strength of the packaged unit of soldered ball and installation base plate by easy method in Japanese Patent Application 2011-144328.The objective of the invention is to, a kind of compositions of thermosetting resin that can be applicable to the method for joining of these packaged unit is provided.
In order to solve above-mentioned problem, the invention provides the compositions of thermosetting resin of the following stated.
That is, compositions of thermosetting resin of the present invention is the compositions of thermosetting resin for the method for joining of packaged unit, and it contains Resins, epoxy, organic acid and thixotropic agent, and described Resins, epoxy contains dimer acid type Resins, epoxy,
The method of joining of described packaged unit possesses following operation:
Film forms operation, and the film that forms the resin combination film forms operation, and this resin combination film is made of compositions of thermosetting resin, and its thickness is more than 20% and below 90% with respect to the height dimension of soldered ball;
Resin combination adheres to operation, and the soldered ball of packaged unit is immersed in the described resin combination film, makes described compositions of thermosetting resin be attached to described soldered ball;
Load operation, the packaged unit that are attached with described compositions of thermosetting resin are loaded in the joint of installation base plate with on the pad; And
The Reflow Soldering operation by the described installation base plate that is mounted with packaged unit is heated, makes described soldered ball fusion, described soldered ball is engaged in the joint pad of described installation base plate.
Compositions of thermosetting resin of the present invention preferably further contains epoxy curing agent.
Compositions of thermosetting resin of the present invention preferably further contains the compound of monofunctional glycidyl base.
For compositions of thermosetting resin of the present invention, the cohesive force when being preferably formed the film of thickness 0.2mm is 2N/m
2More than and 14N/m
2Below, viscosity 40 ℃ of temperature is more than the 20Pas and below the 3000Pas, MV minium viscosity when being warming up to the fusing point of scolding tin with 0.1 ℃/second heat-up rate from 40 ℃ of temperature is below the 1Pas, and is warming up to from 40 ℃ of temperature with 0.1 ℃/second heat-up rate that the viscosity under the scolding tin fusing point is more than the 10000Pas behind the fusing point of scolding tin.
In the method for joining of the packaged unit that the present invention relates to, as described below, can guarantee to have the packaged unit of soldered ball and the bond strength of installation base plate by easy method.
Namely, in the method for joining of the packaged unit that the present invention relates to, before the packaged unit that will have soldered ball are loaded into installation base plate, the soldered ball of described packaged unit is immersed in the resin combination film of given thickness, make compositions of thermosetting resin be attached to described soldered ball.By as above operation, can make described compositions of thermosetting resin only be attached to the soldered ball of described packaged unit, can also make the adhesion amount of described compositions of thermosetting resin even.Therefore, can not produce because of the adhesion amount of the described compositions of thermosetting resin in the described packaged unit and too much packaged unit can't be peeled off such problem from the resin combination film, on the other hand, can not produce the such problem of bond strength that to guarantee described packaged unit and described installation base plate because the adhesion amount of the described compositions of thermosetting resin in the described packaged unit is very few.
In addition, in the method for joining of the packaged unit that the present invention relates to, the packaged unit that are attached with described compositions of thermosetting resin are loaded into after the described installation base plate, carry out the Reflow Soldering operation.So, utilize the heat in the Reflow Soldering operation, spread over described soldered ball with described compositions of thermosetting resin is moistening, and after the moistening expansion of described compositions of thermosetting resin, described compositions of thermosetting resin is solidified, can guarantee the bond strength of described packaged unit and described installation base plate thus.
So, even under the situation of not using underfill etc. that the bonding part is strengthened, also can guarantee to have the packaged unit of soldered ball and the bond strength of installation base plate by easy method.
In addition, the inventor etc. have found following problem: in the method for joining of the packaged unit that the present invention relates to, in the Reflow Soldering operation, compositions of thermosetting resin is applied under the situation of excessive thermal process, can't guarantee the bond strength of described packaged unit and described installation base plate.And, further investigate in order to solve this problem, the result has invented a kind of compositions of thermosetting resin, even this compositions of thermosetting resin applies excessive thermal process to compositions of thermosetting resin in the Reflow Soldering operation, also can guarantee the bond strength of described packaged unit and described installation base plate.
According to the present invention, a kind of compositions of thermosetting resin is provided, even described compositions of thermosetting resin applies under the situation of excessive thermal process compositions of thermosetting resin in the Reflow Soldering operation, also can guarantee the bond strength of described packaged unit and described installation base plate, thereby go for the method for joining of described packaged unit.
Description of drawings
Fig. 1 illustrates the packaged unit that use among the present invention and the sketch chart of resin combination film.
Fig. 2 illustrates the sketch chart that in the present invention soldered ball of packaged unit be impregnated in the state in the resin combination film.
Fig. 3 illustrates the sketch chart that the packaged unit that will be attached with compositions of thermosetting resin in the present invention are loaded into installation base plate state before;
Fig. 4 illustrates the sketch chart that the packaged unit that will be attached with compositions of thermosetting resin in the present invention are loaded into installation base plate and have implemented Reflow Soldering operation state afterwards.
Embodiment
At first, describe based on the embodiment of accompanying drawing to the method for joining of the packaged unit that the present invention relates to.Fig. 1 ~ Fig. 4 is the figure of the method for joining of the packaged unit that the present invention relates to for explanation.
As Fig. 1 ~ shown in Figure 4, the method of joining of the packaged unit that the present invention relates to is be used to making the packaged unit 1 with soldered ball 11 be engaged in the method for joining of the packaged unit of installation base plate 2, and it is that the film that possesses following explanation forms the method that operation, resin combination are adhered to operation, loaded operation and Reflow Soldering operation.
Packaged unit 1 are for having the packaged unit of soldered ball 11, and its pad 13 at a face of base plate for packaging 12 has soldered ball 11.The diameter of above-mentioned soldered ball is not particularly limited, and for example is preferably more than the 0.1mm and below the 0.8mm, more preferably more than the 0.2mm and below the 0.7mm.Diameter at soldered ball is lower than under the situation of described lower limit, existence is difficult to packaged unit are engaged in the tendency of installation base plate because soldered ball is too small, on the other hand, diameter at soldered ball surpasses under the situation of the described upper limit, owing to only also can guarantee the bond strength of packaged unit and installation base plate by the joint that adopts soldered ball, therefore, do not need to adopt the method for joining of packaged unit of the present invention.In addition, the spacing of described soldered ball is not particularly limited, and is preferably more than the 0.2mm and below the 1.5mm, more preferably more than the 0.4mm and below the 1.3mm.Spacing at soldered ball is lower than under the situation of described lower limit, not only be difficult to install packaged unit, and be difficult to control the adhesion amount of compositions of thermosetting resin, therefore, there is the bad tendency of joint that causes soldered ball easily because of excessive adhering to, on the other hand, spacing at soldered ball surpasses under the situation of the described upper limit, owing to only also can guarantee the bond strength of packaged unit and installation base plate by the joint that adopts soldered ball, therefore, not need to adopt the method for joining of packaged unit.
The size of packaged unit 1 is not particularly limited, and the length that for example is preferably one side of packaged unit 1 is the size that 5mm is above and 30mm is following.In addition, the ball count of each packaged unit 1 is not particularly limited, and for example is preferably more than 200 and below 1000.
The scolding tin that uses among the present invention is not particularly limited, and can suit to use known scolding tin.In addition, the fusing point of the scolding tin that uses among the present invention also is not particularly limited, and is preferably more than 130 ℃ usually and below 250 ℃.
Form in the operation at film, as shown in Figure 1, formation thickness (T) is more than 20% and 90% following resin combination film 3 with respect to the height dimension (H) of soldered ball.The thickness of resin combination film (T) is lower than described in limited time following, owing to be attached to the adhesion amount deficiency of the compositions of thermosetting resin of packaged unit, therefore, the bond strength of packaged unit and installation base plate becomes insufficient, on the other hand, the thickness of resin combination film (T) surpasses described going up in limited time, owing to the adhesion amount of the compositions of thermosetting resin that is attached to packaged unit is too much, might produce the problem that packaged unit can't be peeled off from the resin combination film.
The method that forms resin combination film 3 is not particularly limited, and can adopt the method that forms resin combination film 3 as shown in Figure 1 on the supporting mass 4 by compositions of thermosetting resin is coated on.As employed apparatus for coating in this case, for example can enumerate: roller coating machine, curtain are coated with machine, spraying machine, dip coater, rod and are coated with machine, spreadometer, screen process press, mould and are coated with machine, lip coating machine (lip coater), comma doctor knife coater (comma coater), intaglio plate coating machine.Wherein, consider that more preferably roller coating machine, mould are coated with machine, preferred especially roller coating machine from the homogeneity of thickness and to the viewpoint of the application easiness of chip plug-in mounting (chip mount) device.
Adhere in the operation at resin combination, as shown in Figure 2, the soldered ball 11 of packaged unit 1 is immersed in the resin combination film 3, make compositions of thermosetting resin be attached to soldered ball 11.
Under the soldered ball 11 that makes packaged unit 1 is immersed in situation in the resin combination film 3, soldered ball 11 is contacted with supporting mass 4.Like this, because the thickness of resin combination film 3 is even, therefore, can make the adhesion amount of the compositions of thermosetting resin that is attached to soldered ball 11 even.
In loading operation, as shown in Figure 3, the packaged unit 1 that are attached with compositions of thermosetting resin 31 are loaded in the joint of installation base plate 2 with on the pad 21.
Device as being used for loading operation can suit to use known chip inserting apparatus.Need to prove, in the present invention, need before loading operation, implement resin combination and adhere to operation.Therefore, as the device that be used for to load operation, preferred use can be after parts be picked up to be loaded on the installation base plate 2 during implement resin combination and adhere to the device of operation.
Material as engaging with pad 21 can suit to use known conductive material (copper, silver etc.).In addition, as insulating body material 22, can suit to use known insulating body material (glass epoxide body material, polyimide matrix material etc.).
In the Reflow Soldering operation, by the installation base plate 2 that is mounted with packaged unit 1 is heated to make soldered ball 11 fusions, as shown in Figure 4, soldered ball 11 is engaged in the joint pad 21 of installation base plate.
Device as being used for the Reflow Soldering operation can suit to use known reflow soldering.
Heating temperature in the Reflow Soldering operation is according to the fusing point of scolding tin and therefore difference, is not particularly limited, and for example preferred high more than 10 ℃ than the fusing point of scolding tin, more preferably the fusing point than scolding tin is high more than 15 ℃.
Heat-up rate in the Reflow Soldering operation is preferably more than 0.2 ℃/second and below 2.0 ℃/second, more preferably more than 0.4 ℃/second and below 1.8 ℃/second.Heat-up rate is lower than that described down in limited time compositions of thermosetting resin 32 may solidify before the scolding tin fusion, on the other hand, heat-up rate surpasses last prescribing a time limit, and has the moistening expansion of the compositions of thermosetting resin 32 inadequate tendency that becomes.
According to aforesaid embodiment, can obtain effect as described below.
That is, compositions of thermosetting resin 31 only is attached on the soldered ball 11 of packaged unit 1, and can makes the adhesion amount of compositions of thermosetting resin 31 even.Therefore, can not produce the problem that too much packaged unit 1 can't be peeled off from resin combination film 3 because of the adhesion amount of the compositions of thermosetting resin 31 in the packaged unit 1, on the other hand, can not produce the such problem of bond strength that to guarantee packaged unit 1 and installation base plate 2 because the adhesion amount of the compositions of thermosetting resin 31 in the packaged unit 1 is very few.
In addition, utilize the heat in the Reflow Soldering operation, as shown in Figure 3, make the compositions of thermosetting resin 31 after the adhering to of the soldered ball 11 that is attached to packaged unit 1 at soldered ball 11 moistening expansion take place, and, after compositions of thermosetting resin 31 moistening expansions, compositions of thermosetting resin 31 is solidified, make the compositions of thermosetting resin 32 after the curing as shown in Figure 4, thus, can guarantee the bond strength of packaged unit 1 and installation base plate 2.
Like this, even under the situation of not using underfill etc. that the bonding part is strengthened, also can guarantee to have the packaged unit 1 of soldered ball 11 and the bond strength of installation base plate 2 by easy method.
Need to prove, in the above-described embodiment, before above-mentioned loading operation, the joint solder paster printing process of printed solder paste (not shown) on the pad 21 that can further be implemented in installation base plate 2.By such printing process, can further improve packaged unit 1 with soldered ball 11 and the bond strength of installation base plate 2.
As the solder paster that in above-mentioned situation, uses, can suit to use known solder paster.
Then, compositions of thermosetting resin of the present invention is described.That is, compositions of thermosetting resin of the present invention is the compositions of thermosetting resin for the method for joining of above-mentioned packaged unit, and it contains Resins, epoxy, organic acid and thixotropic agent, and described Resins, epoxy contains dimer acid type Resins, epoxy.
Be used for Resins, epoxy of the present invention and must contain dimer acid type Resins, epoxy.As dimer acid type Resins, epoxy, can enumerate: the polycondensate of Resins, epoxy and dimeracid etc., for example can enumerate: YD-171, YD-172 that the jER872 that Mitsubishi chemical Co., Ltd makes, Nippon Steel Chemical Co., Ltd make.Do not contain at compositions of thermosetting resin under the situation of described dimer acid type Resins, epoxy, when in the Reflow Soldering operation, compositions of thermosetting resin being applied excessive thermal process, can't guarantee the bond strength of packaged unit and installation base plate.
As the content of described dimer acid type Resins, epoxy, be more than the 5 quality % and below the 30 quality % with respect to compositions of thermosetting resin 100 quality % preferably, more preferably more than the 10 quality % and below the 20 quality %.The content of dimer acid type Resins, epoxy is lower than described in limited time following, exist in the Reflow Soldering operation tendency that the bond strength when compositions of thermosetting resin applied excessive thermal process reduces, on the other hand, the content of dimer acid type Resins, epoxy surpasses described going up in limited time, because hindering scolding tin, compositions of thermosetting resin engages the tendency that exists the joint that utilizes soldered ball to become difficult easily.
In addition, in the present invention, preferably described dimer acid type Resins, epoxy and the Resins, epoxy beyond it are used in combination.
Resins, epoxy as beyond the above-mentioned dimer acid type can suit to use known Resins, epoxy.As the Resins, epoxy beyond the above-mentioned dimer acid type, for example can enumerate: the Resins, epoxy of bisphenol A-type, Bisphenol F type, biphenyl type, naphthalene type, cresols phenolic varnish type, phenol phenolic varnish type, ester type etc.These Resins, epoxy can use a kind separately, also can be mixed with two or more.In addition, these Resins, epoxy preferably contain and are the resin of liquid at normal temperatures, under situation about using at normal temperatures to the resin of solid, preferably use with the resin combination that is liquid at normal temperatures.In addition, in the type of these Resins, epoxy, effective with respect to drop impact from cured article, and then the good viewpoint of moistening extendability is considered in the reflow process process until the fusing point of scolding tin the time, the bisphenol A-type of preferred naphthalene type, liquid bisphenol A-type, liquid Bisphenol F type, hydrogenated liquid type.
As the content of the Resins, epoxy beyond the above-mentioned dimer acid type, be more than the 20 quality % and below the 80 quality % with respect to compositions of thermosetting resin 100 quality % preferably, more preferably more than the 30 quality % and below the 60 quality %.The content of Resins, epoxy is lower than described in limited time following, owing to can't obtain be used to making the sticking admittedly full intensity of packaged unit, therefore, there is the tendency for the patience reduction of drop impact, on the other hand, the content of Resins, epoxy surpasses described going up in limited time, organic acid in the compositions of thermosetting resin and the content of thixotropic agent reduce, and the speed of epoxy resin cure is postponed, and in reflow process, the packaged unit occurrence positions is offset, and has the tendency of easy poor flow.
As the organic acid that uses among the present invention, can suit to use known organic acid.In such organic acid, consider the preferred diprotic acid with alkylidene group that uses from be difficult for taking place the viewpoint that crystallization separates out with the viewpoint of the solvability excellence of Resins, epoxy and preservation.As such diprotic acid with alkylidene group, for example can enumerate: hexanodioic acid, 2,5-diethyl hexanodioic acid, 2,4-diethyl glutarate, 2,2-diethyl glutarate, 3-methylglutaric acid, 2-ethyl-3-propyl group pentanedioic acid, sebacic acid.Wherein, preferred hexanodioic acid.
As above-mentioned organic acid content, be more than the 1 quality % and below the 25 quality % with respect to compositions of thermosetting resin 100 quality % preferably, more preferably more than the 5 quality % and below the 20 quality %.Organic acid content is lower than described in limited time following, exist owing to the speed that makes epoxy resin cure postpones to cause solidifying bad tendency, on the other hand, organic acid content surpasses described going up in limited time, the tendency that exists the insulating reliability that makes the cured film that compositions of thermosetting resin is solidified to form to reduce.
As the thixotropic agent that uses among the present invention, can suit to use known thixotropic agent.As such thixotropic agent, for example can enumerate: fatty acid amide, hydrogenated castor oil.Wherein, from making compositions of thermosetting resin be attached to the soldered ball of packaged unit and the viewpoint that these parts are loaded in the tack of joint with on the pad time being considered the preferred fatty acid acid amides.
As the content of above-mentioned thixotropic agent, be more than the 0.5 quality % and below the 10 quality % with respect to compositions of thermosetting resin 100 quality % preferably, more preferably more than the 1 quality % and below the 5 quality %.The content of thixotropic agent is lower than described in limited time following, there is following tendency: can't obtain thixotropy, when being immersed in the soldered ball of packaged unit in the resin combination film, not only compositions of thermosetting resin can fully not adhere to, and be loaded in joint sticking power of these parts with on the pad time and also reduce, on the other hand, the content of thixotropic agent surpasses described going up in limited time, compositions of thermosetting resin is difficult to moistening expansion on soldered ball, has the tendency of the insulating reliability reduction of cured film.
Compositions of thermosetting resin of the present invention preferably further contains the compound of monofunctional glycidyl base.In compositions of thermosetting resin of the present invention, by using such compound that contains the monofunctional glycidyl base to substitute the part of above-mentioned Resins, epoxy, can in the various characteristicses such as solidified nature that keep compositions of thermosetting resin, the viscosity in the compositions of thermosetting resin be adjusted into preferred scope.
As the compound that contains the monofunctional glycidyl base that uses among the present invention, can suit to use the known compound that contains the monofunctional glycidyl base.As such compound that contains the monofunctional glycidyl base, for example can enumerate: the methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl base ether, phenylglycidyl ether, 2-ethylhexyl glycidyl ether, the decyl glycidyl ether, the stearyl glycidyl ether, allyl glycidyl ether, 2-Methyl Octyl glycidyl ether, methoxy poly (ethylene glycol) list glycidyl ether, oxyethyl group polyethyleneglycol glycidyl ether, butoxy polyethyleneglycol glycidyl ether, phenoxy group polyethyleneglycol glycidyl ether, to the tert-butyl-phenyl glycidyl ether, the secondary butyl phenenyl glycidyl ether, the n-butylphenyl glycidyl ether, the phenylphenol glycidyl ether, cresyl glycidyl ether, dibromomethylbenzene base glycidyl ether.These compounds that contain the monofunctional glycidyl base can use a kind separately, also can be mixed with two or more.In addition, these contain in the compound of monofunctional glycidyl base, consider from the viewpoint of the adjustment easiness of viscosity, preferred especially phenylglycidyl ether.
Stating in the use under the situation of the compound that contains the monofunctional glycidyl base, as its content, is more than the 5 quality % and below the 50 quality % with respect to compositions of thermosetting resin 100 quality % preferably, more preferably more than the 10 quality % and below the 40 quality %.The content that contains the compound of monofunctional glycidyl base is lower than described in limited time following, there is the effect be difficult to obtain adjust the viscosity of compositions of thermosetting resin, on the other hand, the content that contains the compound of monofunctional glycidyl base surpasses described going up in limited time, has the tendency of various characteristicses such as the solidified nature reduction of compositions of thermosetting resin.
Compositions of thermosetting resin of the present invention preferably further contains epoxy curing agent.
As the epoxy curing agent that uses among the present invention, can suit to use known solidifying agent, for example can use solidifying agent as described below.
As the potentiality solidifying agent, for example can enumerate: Novacure HX-3722, HX-3721, HX-3748, HX-3088, HX-3613, HX-3921HP, HX-3941HP (manufacturing of epoxy company of Asahi Chemical Industry, trade(brand)name).
As aliphatic polyamine class solidifying agent, for example can enumerate: Fujicure FXR-1020, FXR-1030, FXR-1050, FXR-1080 (Fuji changes into Industrial Co., Ltd's manufacturing, trade(brand)name).
As Resins, epoxy amine adduct class solidifying agent, for example can enumerate: Amicure PN-23, PN-F, MY-24, VDH, UDH, PN-31, PN-40 (manufacturing of aginomoto fine chemistry Co., Ltd., trade(brand)name), EH-3615S, EH-3293S, EH-3366S, EH-3842, EH-3670S, EH-3636AS, EH-4346S (Asahi Denka Kogyo K. K's manufacturing, trade(brand)name).
As the imidazoles curing catalyst, for example can enumerate: 2P4MHZ, 2MZA, 2PZ, C11Z, C17Z, 2E4MZ, 2P4MZ, C11Z-CNS, 2PZ-CNZ (above is trade(brand)name).
As the content of above-mentioned epoxy curing agent, be more than the 0.5 quality % and below the 10 quality % with respect to compositions of thermosetting resin 100 quality % preferably, more preferably more than the 1.5 quality % and below the 8 quality %.The content of solidifying agent is lower than and describedly down in limited time has the tendency that thermosetting resin cured speed is postponed easily, and on the other hand, the content of solidifying agent surpasses described going up in limited time, has the reactive tendency that accelerates and shorten duration of service of compositions of thermosetting resin.
Except above-mentioned Resins, epoxy, above-mentioned organic acid, above-mentioned thixotropic agent, the above-mentioned compound and above-mentioned epoxy curing agent that contains the monofunctional glycidyl base, compositions of thermosetting resin of the present invention can also contain additives such as tensio-active agent, coupling agent, defoamer, powder surface treatment agent, reaction control agent, anti-sedimentation agent as required.As these content of additive, be more than the 0.01 quality % and below the 10 quality % with respect to compositions of thermosetting resin 100 quality % preferably, more preferably more than the 0.05 quality % and below the 5 quality %.Content of additive is lower than and describedly down in limited time has the tendency of the effect that is difficult for each additive of performance, and on the other hand, content of additive surpasses described going up in limited time, the tendency that the bond strength that exists compositions of thermosetting resin to bring reduces.
In compositions of thermosetting resin of the present invention, preferably the cohesive force when forming the film of thickness 0.2mm is 2N/m
2More than and 14N/m
2Below, 4N/m more preferably
2More than and 12N/m
2Below.Cohesive force is lower than described in limited time following, there is following tendency: when being loaded in packaged unit on the pad, because confining force temporarily reduces, therefore, not only in the Reflow Soldering operation, cause the position skew easily, and, compositions of thermosetting resin is insufficient to the adhesion amount of soldered ball, therefore, can't guarantee sufficient joint strength, on the other hand, cohesive force surpasses described going up in limited time, compositions of thermosetting resin is attached under the situation of packaged unit, is being easy to generate and packaged unit can't be peeled off such problem from the resin combination film.Need to prove that cohesive force can be measured according to the method for putting down in writing among the JIS-Z3284, particularly, can use cohesion test machine (manufacturing of Marco company, trade(brand)name " TK-1 ") and diameter to measure as the test probe of 5.1mm.
In compositions of thermosetting resin of the present invention, preferably the viscosity (rheometer viscosity) 40 ℃ of temperature is more than the 20Pas and below the 3000Pas.When the viscosity of 40 ℃ of temperature is lower than 20Pas, there is following tendency: when being loaded in packaged unit on the pad, because confining force temporarily reduces, therefore, not only in the Reflow Soldering operation, cause the position skew easily, and compositions of thermosetting resin is insufficient to the adhesion amount of soldered ball, therefore, can't guarantee sufficient joint strength, on the other hand, when the viscosity of 40 ℃ of temperature surpasses 3000Pas, compositions of thermosetting resin is attached under the situation of packaged unit, the such problem that exists easy generation packaged unit can't be peeled off from the resin combination film.In addition, from the operability of compositions of thermosetting resin and have the packaged unit of soldered ball and the viewpoint of the bond strength of installation base plate is considered, be preferably more than the 50Pas and below the 1000Pas in the viscosity of 40 ℃ of temperature, more preferably 100Pas is above and below the 500Pas.Need to prove that the viscosity among the present invention can be measured by the determination of viscoelasticity device.Particularly, can use rheometer (manufacturing of HAAKE company, trade(brand)name " MARS-III ") to measure viscosity according to given condition.
In compositions of thermosetting resin of the present invention, the MV minium viscosity when preferably being warming up to the fusing point of scolding tin with 0.1 ℃/second heat-up rate from 40 ℃ of temperature is below the 1Pas.Be higher than in MV minium viscosity under the situation of 1Pas, exist compositions of thermosetting resin to the moistening expansion of the soldered ball inadequate tendency that becomes.In addition, from compositions of thermosetting resin the viewpoint of the moistening expansion of soldered ball is considered that more preferably MV minium viscosity is more than the 0.1Pas and is lower than 1Pas.
In compositions of thermosetting resin of the present invention, be warming up to from 40 ℃ of temperature with 0.1 ℃/second heat-up rate preferably that the viscosity under the fusing point of scolding tin is more than the 10000Pas behind the fusing point of scolding tin.If viscosity is more than the 10000Pas, can judge that then compositions of thermosetting resin solidifies fully.In addition, as mentioned above, under the situation that is determined at the viscosity under the fusing point of scolding tin, in order stably to measure viscosity, the temperature of compositions of thermosetting resin can be kept constant mensuration more afterwards preset time (for example 10 minutes).
In compositions of thermosetting resin of the present invention, preferably the brookfield viscosity (BF viscosity) 25 ℃ of temperature is 0.8 * 10
3MPas is above and 100 * 10
3Below the mPas.Consider from the viewpoint of the bond strength of packaged unit with soldered ball and installation base plate, in the BF viscosity of 25 ℃ of temperature more preferably 0.8 * 10
3MPas is above and 5 * 10
3Below the mPas.
In addition, in compositions of thermosetting resin of the present invention, thixotropic ratio is not particularly limited, and is preferably more than 2 and below 4.5.
Embodiment
Then, the present invention will be described in more detail by embodiment and comparative example, but the present invention is not subjected to any restriction of these examples.In addition, the material that uses in embodiment and the comparative example below is shown.
Resins, epoxy A: bisphenol A type epoxy resin, trade(brand)name " EPICLON EXA-830LVP ", ADEKA company make
Resins, epoxy B: glycidyl ester type epoxy resin, trade(brand)name " ARALDITE CY-184 ", HUNTSMAN company make
Resins, epoxy C: dimer acid type semi-solid state Resins, epoxy, trade(brand)name " jER872 ", Mitsubishi chemical Co., Ltd make
Resins, epoxy D: naphthalene type Resins, epoxy, trade(brand)name " EPICLON HP-4032b ", DIC company make
The compound that contains the monofunctional glycidyl base: phenylglycidyl ether, trade(brand)name " Denacol EX-141 ", Nagase-Elex company make
Epoxy curing agent: 2 phenyl 4 methyl 5 hydroxy methylimidazole, trade(brand)name " Curezol 2P4MHZ ", four countries change into Co., Ltd. and make
Thixotropic agent: higher fatty acid polymeric amide, trade(brand)name " TALEN VA-79 ", Kyoeisha Chemical Co., Ltd. make
Organic acid: hexanodioic acid, Kanto Electrization Industrial Co., Ltd make
Tensio-active agent: trade(brand)name " BYK361N ", BYK-Chemie Janan company make
Defoamer: trade(brand)name " Floren AC-303 ", Kyoeisha Chemical Co., Ltd. make
[embodiment 1]
Resins, epoxy A 40 quality %, Resins, epoxy B 10 quality %, Resins, epoxy C 10 quality %, the compound 30 quality % that contain the monofunctional glycidyl base, epoxy curing agent 1 quality %, thixotropic agent 2 quality %, organic acid 5 quality %, tensio-active agent 1 quality % and defoamer 1 quality % are put in the container; use mixing and kneading machine to mix, obtained compositions of thermosetting resin.
Then, the compositions of thermosetting resin that obtains is coated on the supporting mass with spreadometer (100 μ m with), has obtained the resin combination film.The thickness of the resin combination film that obtains is 0.2mm.
Then, use chip inserting apparatus (manufacturing of YAMAHA company, trade(brand)name " YV100Xg-F "), pick up the BGA encapsulation (fusing point of size: 17mm * 17mm, ball height: 0.3mm, space between solder balls: 0.5mm, scolding tin: 217 ℃, the composition of scolding tin: 96.5Sn/3Ag/0.5Cu), the soldered ball of BGA encapsulation is immersed in the resin combination film that obtains, makes compositions of thermosetting resin be attached to soldered ball.Need to prove that the thickness of resin combination film is 67% with respect to the ratio of the height dimension 100% of soldered ball.Then, the BGA that is attached with compositions of thermosetting resin is loaded in the joint of installation base plate with on the pad.
Then, the installation base plate that has loaded the BGA encapsulation is heated to 240 ℃ of temperature with reflow soldering (the field village makes the manufacturing of Co., Ltd. of institute, trade(brand)name " TNP "), makes the soldered ball fusion thus, BGA encapsulation and installation base plate are engaged.
[embodiment 2 ~ 4]
Cooperate each material according to the composition shown in the table 1, in addition, operation has obtained compositions of thermosetting resin similarly to Example 1.In addition, use the compositions of thermosetting resin that obtains, in addition, operation similarly to Example 1 engages BGA encapsulation and installation base plate.
[comparative example 1 ~ 6]
Cooperate each material according to the composition shown in the table 2, in addition, operation has obtained compositions of thermosetting resin similarly to Example 1.In addition, use the compositions of thermosetting resin that obtains, in addition, operation similarly to Example 1 engages BGA encapsulation and installation base plate.
(evaluation of the bonding part of compositions of thermosetting resin and packaged unit)
Operability by method as described below during to the loading of the performance (cohesive force, rheometer viscosity, BF viscosity, thixotropic ratio) of compositions of thermosetting resin, packaged unit, and the performance (resistance value, drop impact number of times) of the bonding part of packaged unit and installation base plate carried out estimating or measuring.The results are shown in table 1 and table 2 with what obtain.Need to prove that about comparative example 4 and comparative example 6, the operability when packaged unit load is defective, therefore, can't measure the performance of the bonding part of packaged unit and installation base plate.
(i) brookfield viscosity (BF viscosity)
The viscometer RVT type that uses Brookfield company to make has been measured the BF viscosity of compositions of thermosetting resin 25 ℃ of temperature with speed of mainshaft 50rpm.
(ii) thixotropic ratio
The viscometer RVT type that uses Brookfield company to make has been measured compositions of thermosetting resin with speed of mainshaft 5rpm and has been measured the BF viscosity (η 50) of compositions of thermosetting resin 25 ℃ of temperature in the BF viscosity (η 5) of 25 ℃ of temperature and with speed of mainshaft 50rpm.Then, calculate thixotropic ratio (η 5/ η 50) by these measured values.
(iii) cohesive force
Use the test probe of cohesion test machine (manufacturing of Marco company, trade(brand)name " TK-1 ") and diameter 5.1mm, measured resin combination film (thickness: cohesive force 0.2mm) according to JIS Z3284.
(iv) rheometer viscosity
Use rheometer (HAAKE company makes, trade(brand)name " MARS-III "), on one side be warming up to scolding tin from 40 ℃ of temperature with 0.1 ℃/second heat-up rate fusing point measured the viscosity of compositions of thermosetting resin on one side.Obtain viscosity 40 ℃ of temperature, MV minium viscosity when being warming up to the fusing point of scolding tin with 0.1 ℃/second heat-up rate from 40 ℃ of temperature and the viscosity under the fusing point of back at scolding tin that heat up by the result who obtains.
(the v) operability the during loading of packaged unit
Use chip inserting apparatus (YAMAHA company makes, trade(brand)name " YV100Xg-F "), make the soldered ball of packaged unit be immersed in the resin combination film after, estimate and whether packaged unit can be peeled off from the resin combination film.The situation that packaged unit are peeled off from the resin combination film can be set at " qualified ", the situation that packaged unit are peeled off from the resin combination film can't be judged to be " defective ".
(vi) resistance value
Use digital multimeter (manufacturing of Agilent company, trade(brand)name " 34401A ") to measure the resistance value in the bonding part of packaged unit and installation base plate.In addition, be that situation more than the 1000M Ω is judged to be " can not measure " with resistance value.
(the vii) resistance value after the Reflow Soldering 2 times
Use compositions of thermosetting resin, utilize reflow soldering (the field village makes the manufacturing of Co., Ltd. of institute, trade(brand)name " TNP ") that the installation base plate that is mounted with the BGA encapsulation is heated (temperature: 240 ℃) 2 times continuously, make the soldered ball fusion thus, BGA encapsulation and installation base plate are engaged, with it as sample.By with the same method of the measuring method of the resistance value of above-mentioned record the sample that obtains having been measured resistance value.
(viii) drop impact number of times
Packaged unit are engaged in installation base plate, with it as sample, the drop impact number of times of having measured as described below.That is, sample is fixed on the anchor clamps, connects conducting distribution (resistance value is measured and used), and use digital multimeter (manufacturing of Agilent company, trade(brand)name " 34401A ") to measure the initial stage resistance value.Then, make sample fall and impact from height 100cm, measure the resistance value during this, repeat this operation.Resistance value in falling is reached 4 times number of times of initial stage resistance value as the drop impact number of times.In addition, be that situation more than the 1000M Ω is judged to be " can not measure " with described resistance value.
[table 1]
[table 2]
Can be confirmed by the result shown in table 1 and the table 2, under the situation of having used compositions of thermosetting resin of the present invention (embodiment 1 ~ 8), even carry out continuously 2 Reflow Soldering operations such apply excessive thermal process the time, also can guarantee the bond strength of packaged unit and installation base plate.Relative therewith, to have confirmed using under the situation (comparative example 1 ~ 7) that does not contain the compositions of thermosetting resin of dimer acid type Resins, epoxy, the resistance value after the Reflow Soldering 2 times can not be measured, and can't guarantee the joint of packaged unit and installation base plate.
Claims (5)
1. compositions of thermosetting resin, it is the compositions of thermosetting resin for the method for joining of packaged unit, and this compositions of thermosetting resin contains Resins, epoxy, organic acid and thixotropic agent, and described Resins, epoxy contains dimer acid type Resins, epoxy,
The method of joining of described packaged unit possesses following operation:
The film that forms the resin combination film forms operation, and this resin combination film is formed by compositions of thermosetting resin, and its thickness is more than 20% and below 90% with respect to the height dimension of soldered ball;
Resin combination adheres to operation, and the soldered ball of packaged unit is immersed in the described resin combination film, makes described compositions of thermosetting resin be attached to described soldered ball;
Load operation, the packaged unit that are attached with described compositions of thermosetting resin are loaded in the joint of installation base plate with on the pad; And
The Reflow Soldering operation by the described installation base plate that is mounted with packaged unit is heated, makes described soldered ball fusion, described soldered ball is engaged in the joint pad of described installation base plate.
2. compositions of thermosetting resin according to claim 1 wherein, also contains epoxy curing agent.
3. compositions of thermosetting resin according to claim 1 and 2 wherein, also contains the compound of monofunctional glycidyl base.
4. compositions of thermosetting resin according to claim 1 and 2, wherein,
Cohesive force when forming the film of thickness 0.2mm is 2N/m
2More than and 14N/m
2Below;
Viscosity 40 ℃ of temperature is more than the 20Pas and below the 3000Pas;
MV minium viscosity when being warming up to the fusing point of scolding tin with 0.1 ℃/second heat-up rate from 40 ℃ of temperature is below the 1Pas; And
Be warming up to from 40 ℃ of temperature with 0.1 ℃/second heat-up rate that the viscosity under the scolding tin fusing point is more than the 10000Pas behind the fusing point of scolding tin.
5. compositions of thermosetting resin according to claim 3, wherein,
Cohesive force when forming the film of thickness 0.2mm is 2N/m
2More than and 14N/m
2Below;
Viscosity under 40 ℃ of temperature is more than the 20Pas and below the 3000Pas;
MV minium viscosity when being warming up to the fusing point of scolding tin with 0.1 ℃/second heat-up rate from 40 ℃ of temperature is below the 1Pas; And
Be warming up to from 40 ℃ of temperature with 0.1 ℃/second heat-up rate that the viscosity under the scolding tin fusing point is more than the 10000Pas behind the fusing point of scolding tin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012037815A JP5869911B2 (en) | 2012-02-23 | 2012-02-23 | Thermosetting resin composition |
| JP2012-037815 | 2012-02-23 |
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| CN103289621A true CN103289621A (en) | 2013-09-11 |
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| CN2013100383678A Pending CN103289621A (en) | 2012-02-23 | 2013-01-31 | Thermosetting resin composition |
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| JP (1) | JP5869911B2 (en) |
| KR (1) | KR102000006B1 (en) |
| CN (1) | CN103289621A (en) |
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2012
- 2012-02-23 JP JP2012037815A patent/JP5869911B2/en not_active Expired - Fee Related
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- 2013-01-31 CN CN2013100383678A patent/CN103289621A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| KR102000006B1 (en) | 2019-07-15 |
| JP2013173819A (en) | 2013-09-05 |
| KR20130097099A (en) | 2013-09-02 |
| JP5869911B2 (en) | 2016-02-24 |
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Application publication date: 20130911 |