CN101400715A - Liquid epoxy resin composition and adhesive using same - Google Patents

Liquid epoxy resin composition and adhesive using same Download PDF

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Publication number
CN101400715A
CN101400715A CN200780008387.3A CN200780008387A CN101400715A CN 101400715 A CN101400715 A CN 101400715A CN 200780008387 A CN200780008387 A CN 200780008387A CN 101400715 A CN101400715 A CN 101400715A
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China
Prior art keywords
epoxy resin
resin composition
liquid epoxy
seconds
reactivity
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CN200780008387.3A
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CN101400715B (en
Inventor
谷口昌
渡边裕一
菊池秀树
松村泰男
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Somar Corp
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Somar Corp
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Priority claimed from PCT/JP2007/050614 external-priority patent/WO2007083673A1/en
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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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    • H01L23/00—Details of semiconductor or other solid state devices
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Abstract

A liquid epoxy resin composition containing at least an epoxy resin and a curing agent wherein in preferable, an adhesion strength (A) in the case of the curing at 150 DEG C for 60 seconds and an adhesion strength (B) in the case of the curing at 150 DEG C for 1 hr satisfy the following relationship: 0.6B < A; and an adhesive containing such a liquid epoxy resin composition.

Description

The tackiness agent of liquid epoxy resin composition and use said composition
Technical field
The present invention relates to a kind of liquid epoxy resin composition of surface mounting and tackiness agent that uses said composition of being suitable for, relate in particular to when being fixed to parts such as semi-conductor, electronic unit on the various printed base plates, in very short set time, make the electronic unit that is loaded on the various printed base plates etc. can keep not taking place the state that is shifted or peels off, even and if liquid epoxy resin composition that also can be adhesively fixed reliably for the electronic unit of miniaturization and the tackiness agent that uses said composition.
Background technology
All the time, use the tackiness agent contain composition epoxy resin surface mounting to be fixed on tackiness agent on the printed base plate with adhering components as being used for.As such tackiness agent, for example, disclose contain Resins, epoxy, amine curing agent, (チ キ ソ pays as thixotropic agent Tackiness agent of wetting ability silica microparticle drug) (with reference to patent document 1) and the tackiness agent (with reference to patent document 2) that contains liquid-state epoxy resin, amine potential curing agent, calcination of talc, organic class rheologic additive.
Recently, contain semi-conductive electronic unit and rise to purpose with performances such as the high capacity of data, processing speed high speeds, cost degradation is also pursued in miniaturization gradually, densification on the contrary, and then develops and different in the past electronic units.Because the state on these electronic unit surfaces (adhesive face) is also more and more diversified, therefore use the tackiness agent of record in patent document 1, the patent document 2 and other in the past tackiness agent can not obtain enough adhesive powers sometimes, industrial community urgently wishes to develop the resin combination (tackiness agent) that can bring into play the stable adhesive power that the kind with electronic unit has nothing to do.
But, adopted the measuring method of JIS K 6850 as this kind adhesive power in the past always, comprise the other materials that also used beyond the aluminium as surface mounting during with the weather resistance of the various electronic units of the chip capacitor of parts etc. in evaluation, this method of known use is estimated adhesive power can not obtain credible high evaluation.Therefore, for the various electronic units that contain chip capacitor etc., adopt always and use pull and push dynamometer (push-pull gauge) to carry out method for measuring (with reference to patent document 3,4).Self-evident, expect a kind of tackiness agent that demonstrates the above bond strength of certain level when adopting this method to estimate.
Patent document 1: Japanese kokai publication hei 04-33916 communique
Patent document 2: Japanese kokai publication hei 07-316400 communique
Patent document 3: Japanese kokai publication hei 03-39378 communique
Patent document 4: Japanese kokai publication hei 10-27956 communique
Summary of the invention
The present invention with these problem points as problem, even if promptly, provide a kind of and in short set time, have high adhesive power and also can be adhesively fixed reliably for the electronic unit of miniaturization and can obtain and the liquid epoxy resin composition of the irrelevant enough bond strengths of electronic unit kind and the tackiness agent that uses said composition.
The inventor etc. have carried out deep research for solving the problems of the technologies described above, found that, use contain at least Resins, epoxy and solidifying agent, set time and adhesive power satisfy the tackiness agent of the liquid epoxy resin composition of particular kind of relationship, has high adhesive power at short notice, irrelevant with size and kind, all can obtain high bond strength to various electronic units, thereby finish the present invention.
Known in addition, about liquid epoxy resin composition that is suitable for surface mounting and the tackiness agent that uses said composition, when the performance evaluation of the various electronic units that contain chip capacitor etc., used to be used as the gelation time of testing index set time in the past, thereby the composition with abundant performance can not be provided.As one of its reason, gelation time only shows the index of crosslinked time opening, for the various electronic units that contain chip capacitor etc., usually be about 60 seconds under 150 ℃ the set time of jointing material, thereby, for also can be under this condition to demonstrate the state solidified composition epoxy resin of enough bond strengths, result of study shows, if can satisfy the high composition epoxy resin of initial reaction rate of the relation of stipulating with reactivity described later (reaction rate), then can be irrelevant with size and kind, various electronic units are all obtained high bond strength, thereby finished the present invention.
That is, the invention provides the tackiness agent of following liquid epoxy resin composition and use said composition.
(1) a kind of liquid epoxy resin composition, it contains (a) Resins, epoxy at least, (b) solidifying agent, it is characterized in that, on the substrate that is coated with solder resist (solder mask) and prefluxing (preflux), after using divider that this liquid epoxy resin composition is 2 of 0.7 ± 0.15mm coatings with every coating diameter, to stick at coating place as 2012 type rectangular ceramic electrical condensers of adherend, be stained with make substrate surface temperature be warming up to 150 ℃ in back 30 seconds after, put after keeping making it in 60 seconds or 1 hour solidifying and be chilled to 23 ℃, when testing by bond test, 1 hour adhesive power (B) of adhesive power (A) when 150 ℃ following hold-time of temperature is 60 seconds and maintenance satisfies the relation of formula 0.6B＜A regulation, the intensity when described bond test promotes to peel off with the vertical direction of parts major axis for using pull and push dynamometer to measure the edge.
According to aforementioned (1) described liquid epoxy resin composition, it is characterized in that (2) aforementioned adhesive power (A) is more than the 30N.
(3) according to aforementioned (1) or (2) described liquid epoxy resin composition, it is characterized in that, when each reactivity that makes the liquid epoxy resin composition of curing in the time of 0 second, 30 seconds, 60 seconds, 90 seconds under 150 ℃ the temperature was counted α (0), α (30), α (60), α (90) respectively, their relation was expressed from the next:
[several 1]
X＝[α(30)-α(0)]/[α(90)-α(60)]
(in the formula, X is more than 3, below 15).
(4) according to each described liquid epoxy resin composition in aforementioned (1)～(3), it is characterized in that, when each reactivity that makes the liquid epoxy resin composition of curing in the time of 0 second, 30 seconds, 60 seconds, 90 seconds under 130 ℃ the temperature was counted β (0), β (30), β (60), β (90) respectively, their relation was expressed from the next:
[several 2]
Y＝[β(30)-β(0)]/[β(90)-β(60)]
(in the formula, Y is more than 2, below 10).
(5) according to each described liquid epoxy resin composition in aforementioned (1)～(4), it is characterized in that solidifying the ratio Z (γ (150)/γ (80)) that solidifies 30 seconds reactivity γ (80) under 30 seconds reactivity γ (150) and 80 ℃ the temperature under 150 ℃ the temperature is more than 10.
(6) according to each described liquid epoxy resin composition in aforementioned (1)～(5), it is characterized in that, employing is 5 * 10 according to the bending elastic modulus of the method solidified test film of JIS K 6911 (condition of cure: 120 ℃ following 1 hour, and then 150 ℃ following 1 hour) under 20 ℃ 8～5 * 10 10The scope of Pa.
(7) a kind of tackiness agent is characterized in that, contains each described liquid epoxy resin composition in aforementioned (1)～(6).
Reactivity among the present invention is meant, the differential scanning calorimeter (DSC) that uses Mac Science company described later (now being Bruker AXS company (Japan)) to produce, according to the appended little damp method (Xiao swamp method of DSC of this device) handbook of software derives the response prediction formula, the reactivity under the specified time of calculating based on this formula.In addition, when calculating reactivity, analyze (the rich too サ イ エ of the Lang Zhu Talk Talk society Application テ イ Off イ Star Network of the refreshing Kobe of little Ze husband with new edition heat
Figure A200780008387D0007160448QIETU
), T.OZAWA, J.Thermal Anal.2.301 (1970) is reference.According to the record of above-mentioned handbook, change the heat-up rate of DSC, obtain every physical data, by this data computation reactivity.At this moment, by utilizing in the reactivity of considering each time under bonding operation as tackiness agent, the specified temp that wearing quality adopts, also can in very short set time, be adhesively fixed reliably and have the screening index of the binding compositions of high adhesive power more miniaturization, more highly integrated electronic unit even can be effective as, thereby finish the present invention.The reactivity of trying to achieve with this method with compare as the previous methods of the supposition state of cure of index determining with gelation time, error reduces, particularly as be used for surface mounting such as chip capacitor with parts be adhered fixed tackiness agent on printed base plate and so on, when requiring at short notice to use in the solidified field, can more correctly predict the state of cure in the short period of time, thereby be preferred.
Liquid epoxy resin composition of the present invention and use the tackiness agent of this liquid epoxy resin composition, promptly has rapidly-curable, also have high bond strength, can prevent from simultaneously to follow internal stress to increase and breaking of taking place etc., therefore can improve yield rate and product reliability simultaneously.Like this, liquid epoxy resin composition of the present invention can provide particularly tackiness agent very useful when being surface mounted in electronic unit (comprising semi-conductor) etc. on the printed base plate.
Embodiment
Below, specify liquid epoxy resin composition of the present invention and use the preferred forms of the tackiness agent of this liquid epoxy resin composition, but the present invention is not limited to mode as described below.
[1] Resins, epoxy
As the Resins, epoxy that uses among the present invention, be the resin that has the epoxy group(ing) more than 2 in 1 molecule, for example can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type (phenol novolac) or cresol-novolak type epoxy resin, alicyclic epoxy resin, Hydrogenated Bisphenol A type or AD type Resins, epoxy, propylene glycol diglycidylether, aliphatic category Resins, epoxy such as tetramethylolmethane polyglycidyl ether, the Resins, epoxy that makes by aliphatics or aromatic carboxylic acid and epoxy chloropropane, the Resins, epoxy that makes by aliphatics or aromatic amine and epoxy chloropropane, the heterocyclic ring epoxy resins, the Resins, epoxy that contains volution, epoxy modified resin, bisphenol-s epoxy resin, biphenol (biphenol) type Resins, epoxy etc.Wherein, preferably normal temperature is liquid Resins, epoxy down, even but normal temperature is down solid-state, also can use in the Resins, epoxy for liquid state by it is dissolved under the normal temperature.In addition, these Resins, epoxy can use separately, also can make up more than 2 kinds and use.Consider preferred bisphenol A type epoxy resin and bisphenol f type epoxy resin from the balance of the binding property of cured article, electrical insulating property, mechanical characteristics.The mixture of especially preferred bisphenol A type epoxy resin and bisphenol f type epoxy resin.
[2] solidifying agent
As the solidifying agent that uses in the liquid epoxy resin composition of the present invention, preferably adopt the potentiality solidifying agent.As the potentiality solidifying agent, can enumerate: with microcapsule-type potentiality solidifying agent that comprises solidifying agent such as acid anhydrides, imidazoles, phenolic compound, amides for example under the normal temperature for solid-state modified amine compound by heating activatory solidifying agent and under desired temperature in solubilized or the destructive micro-capsule etc.These solidifying agent can use separately, but consider from the rerum natura aspect of regulating set time (reactivity) and cured article, also can make up more than 2 kinds and use.
Viscosity adjustment aspect during from the adjusting of set time (reactivity) with as tackiness agent is considered, is more preferably used amine potentiality solidifying agent in the above-mentioned solidifying agent.As amine potentiality solidifying agent, can enumerate: 2-heptadecyl imidazoles, 2 phenyl 4 methyl 5 hydroxy methylimidazole, 2-phenyl-4-phenmethyl-5-hydroxy methylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-5-triazine and this 2,4-diamino-6-[2-methylimidazolyl-(1)]-imidazolium compoundss such as tricarbimide adducts of ethyl-5-triazine etc.
As the amine adduct compounds, for example, can use ア ミ キ ユ ア PN-23, ア ミ キ ユ ア PN-40J, ア ミ キ ユ ア MY-24 (to be flavor
Figure A200780008387D0008160527QIETU
Off ア イ Application テ Network ノ company makes.ア ミ キ ユ ア is a registered trademark), various commercially available products such as ノ バ キ ユ ア HX-3721, ノ バ キ ユ ア HX-3741 (be the ケ ミ カ of Asahi Chemical Industry Le ズ company make, ノ バ キ ユ ア is a registered trademark).In addition, as the spiral shell acetal compound, for example, can enumerate CTU, ATU, the CTU guanamines (is flavor
Figure A200780008387D0008160527QIETU
Off ア イ Application テ Network ノ company makes.) etc.Particularly, the solidified nature during, low temperature good from the binding property of cured article and the balance of storage stability are considered preferred amines adducts compounds.
Described potentiality solidifying agent, with Powdered under the normal temperature or be blended in pasty state in the Resins, epoxy etc. and carry out commercially availablely, preferably its mass median diameter is below 15 μ m, more preferably below 10 μ m.If particle diameter surpasses 15 μ m, then reactivity, the bond strength in the short period of time is difficult to improve, thereby is not preferred.Consider from rapidly-curable and fusible aspect, preferably use the following potentiality solidifying agent of 5 μ m.
In addition, the usage ratio of solidifying agent with respect to aforementioned epoxy resins 100 mass parts, is preferably 20～60 mass parts, more preferably the scope of 36～50 mass parts.This be because, if less than 20 mass parts, then solidified nature significantly reduces; If surpass 60 mass parts, then the wet fastness of cured article and electric property reduce, and viscosity significantly rises simultaneously.These potentiality solidifying agent can use separately, also can make up more than 2 kinds and use.In addition, when selecting solidifying agent, consider low-temperature curing speed, when utilizing the bond test that adopts pull and push dynamometer to measure to test, naturally need to select amount fully, so that the adhesive power (A) and the relation that satisfies formula 0.6B＜A defined of the adhesive power (B) during maintenance in 1 hour of 150 ℃ following hold-time of temperature when being 60 seconds.When being used in combination more than 2 kinds, need in the solidifying agent total amount, occupy more than the preferred at least 50 quality % at 150 ℃ of solidifying agent that have 50% above reactivity in following 30 seconds according to making when only using a kind of solidifying agent, more preferably the ratio of 60 quality % is selected solidifying agent.In addition, because the curing speed of Dyhard RU 100 class solidifying agent under 150 ℃ is generally slower, so, preferably do not use Dyhard RU 100 class solidifying agent as main solidifying agent raw material for composition of the present invention.Certainly, as long as within the scope that satisfies as the important document of composition of the present invention,, certainly add Dyhard RU 100 class solidifying agent for the purpose that improves storage stability, enhancing adhesive strength.
[3] other compositions
In the liquid epoxy resin composition of the present invention, can add other additives as required.As additive, for example, can enumerate: fused silica (silica), the crystallinity silica, low alpha-ray silica, glass flake, granulated glass sphere, the glass capsule, talcum, aluminum oxide, Calucium Silicate powder, aluminium hydroxide, lime carbonate, barium sulfate, magnesium oxide, silicon nitride, inorganic fillers such as boron nitride, comprise acrylic resin or polyester resin, the weighting agent of resin particles such as silicon resinoid, at least has an epoxy group(ing) in the molecule, be low viscous compound at normal temperatures and pressures, phenyl glycidyl ether is specifically arranged, Polyethylene Glycol Bisglycidyl Ether, the polypropylene glycol glycidyl ether, methyl glycidyl ether, propyl glycidyl ether, the tetramethylolmethane polyglycidyl ether, the sorbyl alcohol polyglycidyl ether, n-butyleneglycol glycidyl ether, 2-ethylhexyl glycidyl ether isoreactivity thinner, the phosphorus compound of triphenyl phosphorus etc., as triethylamine, the tetrem hydramine, 1,8-diaza-two ring [5.4.0]-7-undecylene (DBU), N, the N-dimethyl benzylamine, 1,1,3, the 3-tetramethyl guanidine, 2-ethyl-4-methylimidazole, the tertiary amine compounds of N-methyl piperidine etc., for example 1, curing catalysts such as boron compound such as 8-diaza-two ring [5.4.0]-7-undecenyl tetraphenyl boric acid ester, nitrile rubber, divinyl rubber equipressure negative catalyst, silane coupling agent, titante coupling agent, coupling agents such as aluminium class coupling agent, tinting material such as dyestuff and pigment, antioxidant, the wet fastness rising agent, thixotropic agent, thinner, defoamer, levelling agent and other various resins.
Wherein, for improving the viscosity adjustment of composition, particularly using silk screen printing and divider with liquid epoxidation resin combination of the present invention during as adhesive coated, reactive diluent is effective.In addition, consider, preferably use silane coupling agent from the binding property aspect of Resins, epoxy and weighting agent.The cooperation ratio of reactive diluent can suitably be selected according to the viscosity of target tackiness agent, usually with respect to Resins, epoxy 100 mass parts, is the scope of 0～20 mass parts.In addition, the cooperation ratio of coupling agent is the scope of 0.25～2.0 mass parts with respect to weighting agent 100 mass parts usually.But, also can be with the surface of weighting agent in advance with using after the coupling agent treatment.
Liquid epoxy resin composition of the present invention can obtain by the various additives such as weighting agent of blending epoxy, solidifying agent, adding as required, and tackiness agent of the present invention contains the liquid epoxy resin composition that is made of these compositions.
The liquid epoxy resin composition that constitutes by above-mentioned Resins, epoxy, solidifying agent and the various additives such as weighting agent selected for use as required, when utilizing following bond test to test, the adhesive power (A) after 60 seconds and the relation of the adhesive power after 1 hour (B) satisfy 0.6B＜A.The present invention finds, as long as have the adhesion characteristic that can satisfy this relation, the tackiness agent that uses when then comprising various electronic units such as chip capacitor as production just has sufficient practicality with the liquid epoxy resin composition of raw material, has finished the present invention based on this fact.
Promptly, the present invention finds, usually, as being used for surface mounting assembly is adhered fixed tackiness agent on printed base plate, consider its productivity, need and can in the short period of time about 150 ℃, 60 seconds, solidify, at this moment, if reactivity is not high enough to a certain degree, then might be able to not satisfy the level that requires of wet fastness etc., thereby, need to solidify usually the intensity more than at least 50%, the preferred intensity more than 60% that finishes the bond strength after 1 hour, thereby finish the present invention.
[bond test]
Is 0.7 ± 0.15mm be coated with 2 after, will as 2012 type rectangular ceramic electrical condensers of adherend to be installed in said composition on divider at the coating diameter with 1 on the substrate that is coated with solder resist and prefluxing with liquid epoxy resin composition.After rising to 150 ℃ with 30 seconds surface temperatures after the installation with substrate, keep making curing in 60 seconds or 1 hour, put then and be chilled to 23 ℃, with pull and push dynamometer measure along and the intensity of the vertical direction of parts major axis when promoting to peel off.
Relation by aforementioned adhesive power satisfies 0.6B＜A, thereby can obtain adhesive power to a certain degree, even if described degree is for also making nothings such as electronic unit and be shifted or entering subsequent processing with peeling off in shorter set time, do not satisfy at adhesive power under the situation of described relation, need the long time to the set time that obtains till the required adhesive power, thereby the productivity reduction, so be not preferred.Especially when being surface mounted to electronic unit etc. on the printed base plate, owing to preferably reach required strength level at short notice, thereby the adhesive power (A) after preferred 60 seconds is more than the 30N, more preferably more than the 40N.
In addition, liquid epoxy resin composition of the present invention, when each reactivity of the liquid epoxy resin composition when solidifying 0 second, 30 seconds, 60 seconds, 90 seconds down with 150 ℃ was counted α (0), α (30), α (60), α (90) respectively, preferably their relation (X) satisfied following formula (I).Satisfy in the liquid epoxy resin composition of this relation, the influence that is subjected to surrounding environment during curing operation still less and can be brought into play the above adhesive power of certain level in the short period of time, thereby is preferred.
[several 3]
X＝[α(30)-α(0)]/[α(90)-α(60)] (I)
(in the formula, X is more than 3, below 15)
At this moment, though its reason is definite as yet, if the wet fastness and the insulativity of 3 cured articles of X value less than are low; It is too fast to surpass 15 curing speeds, and cured article deforms easily.Consider from the aspect of wet fastness, insulativity and the distortion inhibition of cured article, preferably in 5～15 scope.
And then, liquid epoxy resin composition of the present invention, when each reactivity of the liquid epoxy resin composition of curing in the time of 0 second, 30 seconds, 60 seconds, 90 seconds under 130 ℃ the temperature was counted β (0), β (30), β (60), β (90) respectively, preferably their relation (Y) satisfied following formula (II).This be because, satisfy in the bonding operation that the composition of relation like this is adapted at operating the particular semiconductor packing that guarantees that temperature is lower and use.
[several 4]
Y＝[β(30)-β(0)]/[β(90)-β(60)] (II)
(in the formula, Y is more than 2, below 10)
At this moment, the wet fastness of 2 cured articles of Y less than and insulativity reduce, and it is too fast to surpass 10 curing speeds, and cured article deforms easily.Consider from the aspect of wet fastness, insulativity and the distortion inhibition of cured article, be preferably 2～7 scope.
The X that concerns that liquid epoxy resin composition of the present invention satisfies the reactivity of each time under aforementioned 150 ℃ gets final product, but, in recent years, from comprising the viewpoint of environmental problems such as Global warming and save energy, solidification value has the tendency of reduction, therefore, by the reactivity of the lower temperature of control, especially 130 ℃ of liquid epoxy resin compositions down, the satisfied Y that concerns of reactivity of each time point, thereby no matter can obtain solidification value is high temperature or low temperature, the liquid epoxy resin composition that binding property, solidified nature are all good, thereby be preferred.
The ratio Z (γ (150)/γ (80)) of reactivity γ (80) when the reactivity γ (150) when in addition, liquid epoxy resin composition of the present invention preferably solidifies 30 seconds under 150 ℃ solidifies 30 seconds down with 80 ℃ is more than 10.If ratio less than 10, then 80 ℃ of following reactions just begin to carry out, thereby keeping quality is low, and perhaps 150 ℃ of reactivities after following 60 seconds reduce, that is, during preservation and/or the stability when using reduce, thereby be not preferred.Consider from prolonged preservation and binding property, rapidly-curable aspect, be preferably more than 12 especially.
The X value of trying to achieve in the aforementioned formula (I) more than 3, below 15, the Y value of trying to achieve in the aforementioned formula (II) is more than 2, below 10, and the ratio Z of the reactivity of 150 ℃ reactivity and 80 ℃ is the liquid epoxy resin composition more than 10, because its initial stage (0 second～30 seconds) reactivity height, therefore after 60 seconds, be easy to obtain high adhesive power, and because 80 ℃ the low thereby prolonged preservation excellent in stability of reactivity.Its result is, the tackiness agent that contains this liquid epoxy resin composition is the storage stability height not only, and also can be at short notice that adherends such as electronic unit is bonding securely when using, to have taken into account these two kinds of reverse effects of keeping quality and binding property than the highland level.
And then, liquid epoxy resin composition of the present invention preferably the Young's modulus in the test of following elastic modulus detection 5 * 10 8～5 * 10 10In the scope of Pa.
[bending elastic modulus test]
Method according to JIS K 6911 is measured bending elastic modulus.And, test film use 120 ℃ solidify 1 hour after again at 150 ℃ of samples that solidify 1 hour.
Bending elastic modulus less than 5 * 10 8Pa and when using as tackiness agent, in the occurrence positions skews easily such as electronic unit that upper surface of base plate is installed, its possibility of result produces detrimentally affect to product quality such as malfunctions, in addition, if surpass 5 * 10 10Electronic unit etc. then may take place and come off owing to impacting in Pa easily, causes the product quality variation, thereby is not preferred.Consider that from the product quality aspect preferred elastomeric modulus is 1 * 10 9～7 * 10 9In the scope of Pa.
[4] tackiness agent
Tackiness agent of the present invention can obtain by aforementioned epoxy resins, solidifying agent, the various additives such as weighting agent that use are as required mixed according to a certain percentage, if Resins, epoxy can be formed by directly mixing when being liquid at normal temperatures, if Resins, epoxy at normal temperatures when solid-state can with Resins, epoxy or all composition uniform mixing in solvent make, but consider from the solidified nature aspect of storage stability and short period of time, preferably preparation in accordance with the following methods.
(1) with liquid-state epoxy resin or Resins, epoxy, solidifying agent and the weighting agent etc. that are dissolved in organic solvents such as toluene, ethanol, cellosolve, tetrahydrofuran (THF), N-N-methyl-2-2-pyrrolidone N-, dimethyl formamide in advance be filled in the stirrer (employed stirrer when for example planetary-type mixer or omnipotent stirrer etc. were made tackiness agent in the past).
(2) uniform mixing under the temperature condition of 5～40 ℃ of mixing temperatures, preferred room temperature (about 23 ℃).In addition, as the weighting agent preferred silica, the use level of this moment can suitably be selected according to the alkalescence of solidifying agent, usually with respect to solidifying agent 1 mass parts, is more than 0.05 mass parts, is preferably the scope of 0.07～0.5 mass parts.If use level less than 0.05 mass parts of silica had then both made and added silica and also be difficult to dispersiveness that obtains homogeneous etc., thereby has been not preferred, in addition, use level is too much not preferred yet.
Tackiness agent of the present invention is transcribed various coating processes such as mode, screen printing mode applicable to (dispense) mode of distribution, point.As example, use the fixing means of the electronic unit of tackiness agent of the present invention with the distribution means explanation.
(1) coating of tackiness agent
In the installation position of the electronic unit of substrate, use the divider coating adhesive with schematic circuit.As divider, can be any one mode of bolt type (discharging the mode of tackiness agent by the rotation of bolt), air type (with the mode of air pressure discharge).
(2) electronic unit is fixing
Then, electronic unit is placed in the aforementioned adhesion agent, is solidifying about 30～60 seconds fixing part under 130～180 ℃ the temperature.
When using tackiness agent of the present invention, because adhesive power and/or the reactivity height of heating in back 60 seconds, can be in short set time fixing electronic unit reliably, thereby yield rate height, and owing to can shorten the time that enters next process, so the equal excellence of working efficiency, productivity.In addition, at next process, for example welding is flooded in (solder dipping) operation, because the not change of the shape of tackiness agent, so can suppress the generation of electronic unit inclination, displacement etc., and because difficult suction can prevent that also electric property from descending.
Embodiment
Below, use embodiment to specify liquid epoxy resin composition of the present invention and the tackiness agent that uses this liquid epoxy resin composition, but the tackiness agent of liquid epoxy resin composition of the present invention and this liquid epoxy resin composition of use is not limited to these embodiment.
In addition, for the tackiness agent of embodiment and comparative example, 3 projects of adhesive power, reactivity, Young's modulus have been estimated.These projects adopt following method to estimate.
[adhesive power (N)]
Scribbling solder resist and scribbling on the substrate of prefluxing in advance thereon, is that 0.7 ± 0.15mm be coated with 2 points with liquid epoxy resin composition of the present invention (tackiness agent) with any coating diameter with divider.On this tackiness agent, install after the 2012 type rectangular ceramic electrical condensers, in 30 seconds substrate surface temperature is risen to 150 ℃, keep 60 seconds (A) and 1 hour (B) to make it to solidify (curing oven: state type reflow furnaces SAR-401A (former electric corporation system difficult to understand)) then.(A) and test film (B) put be chilled to room temperature (23 ℃), with pull and push dynamometer measure along and the stripping strength of the vertical direction of parts major axis when promoting.Component count is made as 10, writes down its mean value.
[reactivity]
Calculate according to following steps.
＜1〉differential scanning calorimeter (the differential scanning calorimeter DSC3100/3200 that uses Mac Science company to make), install the record of appended handbook according to this, constant heatingrate's data (5 ℃/minute of heat-up rates according to various samples, 10 ℃/minute, 20 ℃/minute) calculate the velocity of variation of the heat, peak temperature and the peak value that reach whole peak.Here said velocity of variation is that heat when reaching peak temperature is divided by the value of the heat gained at whole peak.
＜2〉the denary logarithm value with above-mentioned heat-up rate is the longitudinal axis, and the inverse of peak temperature is a transverse axis, makes little damp curve (ozawa plot), obtains activation energy, frequency factor and the reaction times of each sample then.
＜3〉according to above-mentioned＜2〉in activation energy, frequency factor and the reaction times of trying to achieve make response prediction figure, obtain the reactivity after 0 second, 30 seconds, 60 seconds and 90 seconds at each temperature of 80 ℃, 130 ℃ and 150 ℃ according to this figure.
＜4〉and then, according to each reactivity after 0 second, 30 seconds, 60 seconds and 90 seconds, obtain 150 ℃ X as a result and 130 ℃ Y as a result according to following formula.
[formula 5]
X or Y=(reactivity-0 when solidifying in 30 seconds second time reactivity)/(reactivity the when reactivity-60 when solidifying in 90 seconds second is solidified)
＜5〉obtain the reactivity of 150 ℃ of following curing in the time of 30 seconds and the ratio Z (150 ℃/80 ℃) of the reactivity of 80 ℃ of following curing in the time of 30 seconds.
[bending elastic modulus (Pa)]
Measure according to JIS K 6911.In addition, test film uses 120 ℃ to solidify the sample that curing made in 1 hour under 150 ℃ again after 1 hour down.
Embodiment 1
(Japanese Epoxy resins company produces, trade(brand)name: Epikote828) 50 mass parts, bisphenol f type epoxy resin 50 mass parts, solidifying agent (imidazoles amine adduct solidifying agent, flavor with bisphenol A type epoxy resin
Figure A200780008387D0008160527QIETU
Off ア イ Application テ Network ノ company makes, trade(brand)name: ア ミ キ ユ ア PN-H, median size 10 μ m) (Japanese ア エ ロ ジ Le company produces, and trade(brand)name: ア エ ロ ジ Le #300) 3 mass parts mix, and make epoxy resin solution for 35 mass parts and silica powder.Afterwards, (primary particle size: about 10nm) 7 mass parts are mixed with refiner as thixotropic agent, the preparation liquid epoxy resin composition to wherein adding silica powder.The liquid epoxy resin composition that obtain this moment can be used as tackiness agent and uses.Its rerum natura is as shown in table 1.
Embodiment 2
Except the solidifying agent among the embodiment 1 being changed to imidazoles amine adduct solidifying agent (flavor
Figure A200780008387D0008160527QIETU
Off ア イ Application テ Network ノ company produces, trade(brand)name: ア ミ キ ユ ア PN-23J, median size is 3 μ m) 20 mass parts and aliphatics amine amine adduct (flavor
Figure A200780008387D0008160527QIETU
Off ア イ Application テ Network ノ company produces, trade(brand)name: ア ミ キ ユ ア MY-24, median size is 8～10 μ m) outside 15 mass parts, other are identical with embodiment 1, prepare the tackiness agent that is made of liquid epoxy resin composition.Its rerum natura is as shown in table 1.
Embodiment 3
Except the solidifying agent among the embodiment 1 being changed to imidazoles amine adduct solidifying agent (flavor
Figure A200780008387D0015101340QIETU
Off ア イ Application テ Network ノ company produces, trade(brand)name: ア ミ キ ユ ア PN-23, median size is 10 μ m) 30 mass parts and aliphatics amine amine adduct class solidifying agent (flavor
Figure A200780008387D0015101345QIETU
Off ア イ Application テ Network ノ company produces, trade(brand)name: ア ミ キ ユ ア MY-24, median size is 8～10 μ m) outside 10 mass parts, other are identical with embodiment 1, prepare the tackiness agent that is made of liquid epoxy resin composition.Its rerum natura is as shown in table 1.
Embodiment 4
Except the solidifying agent among the embodiment 1 being changed to imidazoles amine adduct solidifying agent (flavor Off ア イ Application テ Network ノ company produces, trade(brand)name: ア ミ キ ユ ア PN-40J, median size is 3 μ m) 30 mass parts and aliphatics amine amine adduct class solidifying agent (flavor Off ア イ Application テ Network ノ company produces, trade(brand)name: ア ミ キ ユ ア MY-24, median size is 8～10 μ m) outside 10 mass parts, other are identical with embodiment 1, prepare the tackiness agent that is made of liquid epoxy resin composition.Its rerum natura is as shown in table 1.
Embodiment 5
(the ケ ミ カ of Asahi Chemical Industry Le ズ company makes except the solidifying agent among the embodiment 1 being changed to the microcapsule-type solidifying agent, trade(brand)name: ノ バ キ ユ ア HX-3722, median size is 2 μ m) outside 35 mass parts, other are identical with embodiment 1, the tackiness agent that preparation is made of liquid epoxy resin composition.Its rerum natura is as shown in table 1.
Comparative example 1
Except the solidifying agent among the embodiment 1 being changed to imidazoles amine adduct solidifying agent (flavor Off ア イ Application テ Network ノ company produces, trade(brand)name: ア ミ キ ユ ア PN-40J, median size is 3 μ m) 10 mass parts and aliphatics amine amine adduct (flavor Off ア イ Application テ Network ノ company produces, and commodity be called ア ミ キ ユ ア MY-24, and median size is 8～10 μ m) beyond 30 mass parts, other are identical with embodiment 1, prepare the tackiness agent that is made of liquid epoxy resin composition.In addition, in the said composition, the amount of the ア ミ キ ユ ア PN-40J of curability at low temperatures is lacked than the amount that shows the curability at low temperatures solidifying agent ア ミ キ ユ ア MY-24 of solidified nature under higher temperature, be no more than 25 quality % of whole curing dose, so the adhesive power of said composition relation does not satisfy 0.6B＜A.Its rerum natura is as shown in table 1.
Comparative example 2
(the ケ ミ カ of Asahi Chemical Industry Le ズ company produces except the solidifying agent among the embodiment 1 being changed to Dyhard RU 100 class microcapsule-type solidifying agent, trade(brand)name: ノ バ キ ユ ア HX-3613, median size is 5 μ m) outside 35 mass parts, other are identical with embodiment 1, the tackiness agent that preparation is made of liquid epoxy resin composition.Its rerum natura is as shown in table 1.
[table 1]
According to table 1 as can be known, tackiness agent of the present invention and comparative example 1 are compared adhesive power height at short notice with 2.In addition, the tackiness agent of embodiment 1～5 is compared with 2 with comparative example 1,80 ℃ following time the reactivity Be Controlled get lower.Therefore, storage stability improves, and moment curing reaction takes place when using, and can obtain firm adhesive power in the short period of time.Therefore yield rate improves, and can obtain high-quality product.
Industrial usability
Liquid epoxy resin composition of the present invention and use the sticking of this liquid epoxy resin composition Mixture can be fixed on semiconductor, electronic unit etc. on the circuit substrate at short notice, can Shorten entering the time of subsequent processing, thereby can increase work efficiency and productivity, and can To obtain high bonding of storage stability. If use such adhesive to produce, then can Improve yield rate, obtain high-quality product. So, liquid-state epoxy resin combination of the present invention Thing and use the adhesive of this liquid epoxy resin composition in the installation of semiconductor, electronic unit The field is very effective.

Claims (7)

1. liquid epoxy resin composition, it contains (a) Resins, epoxy, (b) solidifying agent at least, it is characterized in that,
On the substrate that is coated with solder resist and prefluxing, after using divider that this liquid epoxy resin composition is 2 of 0.7 ± 0.15mm coatings with every coating diameter, to stick at coating place as 2012 type rectangular ceramic electrical condensers of adherend, be stained with make substrate surface temperature be warming up to 150 ℃ in back 30 seconds after, put after keeping making it in 60 seconds or 1 hour solidifying and be chilled to 23 ℃, when testing by bond test, adhesive power (A) when 150 ℃ following hold-time of temperature is 60 seconds satisfies the relation that formula 0.6B＜A stipulates with the adhesive power (B) of maintenance in the time of 1 hour, the intensity when described bond test is peeled off with the vertical direction promotion of parts major axis for using pull and push dynamometer to measure the edge.
2. the described liquid epoxy resin composition of claim 1 is characterized in that, aforementioned adhesive power (A) is more than the 30N.
3. claim 1 or 2 described liquid epoxy resin compositions, it is characterized in that, when each reactivity that makes the liquid epoxy resin composition of curing in the time of 0 second, 30 seconds, 60 seconds, 90 seconds under 150 ℃ the temperature was counted α (0), α (30), α (60), α (90) respectively, their relation was expressed from the next:
[several 1]
X＝[α(30)-α(0)]/[α(90)-α(60)]
In the formula, X is more than 3, below 15.
4. each described liquid epoxy resin composition in the claim 1～3, it is characterized in that, when each reactivity that makes the liquid epoxy resin composition of curing in the time of 0 second, 30 seconds, 60 seconds, 90 seconds under 130 ℃ the temperature was counted β (0), β (30), β (60), β (90) respectively, their relation was expressed from the next:
[several 2]
Y＝[β(30)-β(0)]/[β(90)-β(60)]
In the formula, Y is more than 2, below 10.
5. each described liquid epoxy resin composition in the claim 1～4, it is characterized in that the ratio Z (γ (150)/γ (80)) of the reactivity γ (80) when solidifying 30 seconds under reactivity γ (150) when solidifying 30 seconds under 150 ℃ the temperature and 80 ℃ the temperature is more than 10.
6. each described liquid epoxy resin composition in the claim 1～5 is characterized in that, adopting the bending elastic modulus of method solidified test film under 20 ℃ according to JIS K6911 is 5 * 10 8～5 * 10 10The scope of Pa, described condition of cure be 120 ℃ following 1 hour, and then 150 ℃ following 1 hour.
7. a tackiness agent is characterized in that, contains each described liquid epoxy resin composition in the claim 1～6.
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Publication number Priority date Publication date Assignee Title
CN103987802A (en) * 2011-12-15 2014-08-13 迪睿合电子材料有限公司 Adhesive agent, and method for connecting electronic component
CN106987095A (en) * 2017-05-16 2017-07-28 广东博汇新材料科技股份有限公司 High transparency epoxy resin composition for prepreg and preparation method thereof
CN107111193A (en) * 2015-05-20 2017-08-29 积水化学工业株式会社 Sealing material for liquid crystal display device, up and down conductive material and liquid crystal display cells
CN111518499A (en) * 2020-06-08 2020-08-11 武汉市三选科技有限公司 Underfill adhesive with stable adhesive force at high temperature and preparation method thereof

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CN103987802A (en) * 2011-12-15 2014-08-13 迪睿合电子材料有限公司 Adhesive agent, and method for connecting electronic component
CN107111193A (en) * 2015-05-20 2017-08-29 积水化学工业株式会社 Sealing material for liquid crystal display device, up and down conductive material and liquid crystal display cells
CN106987095A (en) * 2017-05-16 2017-07-28 广东博汇新材料科技股份有限公司 High transparency epoxy resin composition for prepreg and preparation method thereof
CN111518499A (en) * 2020-06-08 2020-08-11 武汉市三选科技有限公司 Underfill adhesive with stable adhesive force at high temperature and preparation method thereof

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JP2013100525A (en) 2013-05-23
JPWO2007083673A1 (en) 2009-06-11

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