CN105585937A - Epoxy resin composition - Google Patents
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- CN105585937A CN105585937A CN201510738266.0A CN201510738266A CN105585937A CN 105585937 A CN105585937 A CN 105585937A CN 201510738266 A CN201510738266 A CN 201510738266A CN 105585937 A CN105585937 A CN 105585937A
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Abstract
The invention relates to an epoxy resin composition. In existing epoxy resin composition, high storage stability and low-temperature short-time curing cannot be simultaneously achieved. Because of factors of heat in heating or in reaction, heat in heating or in reaction, shape change after change or flow caused by generated fluidity, a coating shape cannot be sustained. The epoxy resin composition comprises the components of (A)-(E). Furthermore relative to 100 by mass parts of (A), the epoxy resin composition comprises 25-95 by mass parts of (B), 1-20 by mass parts of (C), 5-25 by mass parts of (D), and 0.01-5 by mass parts of (E); wherein (A) is epoxy resin, (B) is polythiol compound, (C) is curing initiator, (D) is amorphous silicon dioxide which is except for Polydimethylsiloxane and performs specific chemical modification, R independently represent alkyls, and sum of numbers of carbon atoms in general formulae (3-5) is above 3; and (E) is reaction inhibitor.
Description
Technical field
The present invention relates to a kind of epoxy resin taking poly-thiol compound as curing agent.
Background technology
In the past, as recorded in patent documentation 1 document such as grade, at CMOS (ComplementaryMetal-Oxide-Semiconductor, complementary metal oxide semiconductors (CMOS)) sensor camera module (cameraModule), in assembling, the two of heat-curing type composition epoxy resin or room temperature curing type have been widely usedComponent epoxy composition. But, in when assembling, must be with high accuracy control composition epoxy resinCoating weight etc. And, in the electronic units such as camera module, from the skew of the parts in when heating or to electronicsThe dysgenic aspect that parts itself cause considers, most preferably under low temperature (80 DEG C with inferior), with shorterTime (10 minutes with interior etc.) is solidified composition epoxy resin. In addition, if comprise in composition epoxy resin to comeFrom the low-molecular-weight annular siloxane ((SiO (CH of raw material3)2)n, n=3～20), when curing, can volatilizeAnd be attached to the unfavorable condition on sensor.
It is known to the such resin with epoxy radicals of patent documentation 2 and the composition of poly-thiol compound,But because its solidfied material is soft, be therefore not suitable for the precision assembling of electrical and electronic parts. And, if epoxyResin (host) has flexible structure, and curing rate is slow, add hanker composition easily flow. In addition, shouldThe not open technology as controlled coating shape of document.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-213146 communique
Patent documentation 2: TOHKEMY 2013-224373 communique
Summary of the invention
Invent problem to be solved
In existing composition epoxy resin, be difficult to have concurrently between storage stability and low-temperature short-time and solidify, because ofHeat when heating or the heating in when reaction, the shape after coating changes or produces mobility and flow etc.,And be difficult to maintain coating shape.
For solving the method for problem
The inventor conducts in-depth research in order to achieve the above object, and result is sent out in composition epoxy resinShow and maintained coating shape and there will not be the shape after coating change or produce mobility and mobile sideMethod, thus the present invention completed.
Next, main idea of the present invention is described. The first embodiment of the present invention relates to a kind of epoxyResin combination, described composition epoxy resin comprises (A)～(E) composition, and with respect to (A) of 100 mass partsComposition, (B) composition that comprises 25～95 mass parts, (C) composition of 1～20 mass parts, 5～25 mass parts(D) (E) composition of composition and 0.01～5 mass parts,
(A) composition is epoxy resin;
(B) composition is poly-thiol compound;
(C) composition is curing accelerator;
(D) composition be except polydiorganosiloxanepolyurea, show by any in following general formula 3～5The group showing has carried out the amorphous silica of chemical modification,
Wherein, R represents respectively alkyl independently, the carbon number of the R in general formula 3～5 various totalMeter is more than 3;
(E) composition is reaction suppressor.
The second embodiment of the present invention relates to the composition epoxy resin described in a kind of the first embodiment, itsIn, the thixotropic ratio of described composition epoxy resin is more than 4.0.
The 3rd embodiment of the present invention relates to the epoxy resin combination described in a kind of first or second embodimentThing, wherein, described (C) composition is epoxy additive compound.
The 4th embodiment of the present invention relates to the epoxy described in any one in a kind of the first～three embodimentResin combination, wherein, described (E) composition be from phosphoric acid, butyl borate, trimethoxy boroxin withAnd in methyl tosylate, select at least one.
The 5th embodiment of the present invention relates to the epoxy described in any one in a kind of the first～four embodimentResin combination, wherein, described (D) composition is except polydiorganosiloxanepolyurea, by following formula 6Or the represented group of formula 7 amorphous silica that carried out chemical modification.
The 6th embodiment of the present invention relates to the epoxy described in any one in a kind of the first～five embodimentResin combination, wherein, described (A) composition is the epoxy resin with bis-phenol skeleton.
The 7th embodiment of the present invention relates to the epoxy described in any one in a kind of the first～six embodimentResin combination, wherein, described (B) composition is the functional group in molecule with plural following formula 2Poly-thiol compound.
The 8th embodiment of the present invention relates to the epoxy described in any one in a kind of the first～seven embodimentResin combination, wherein, described composition epoxy resin is for the assembling of camera module.
Invention effect
In composition epoxy resin of the present invention, suppress the generation of low-molecular-weight annular siloxane, have concurrentlySolidifying under between storage stability and low-temperature short-time, the heating when heat while having suppressed because of heating or reaction is ledShape after the coating causing changes or produces mobility and flow, and can maintain coating shape. ThisBright composition epoxy resin is particularly suitable for the electronic units such as camera module.
Detailed description of the invention
In this manual, " X～Y " of expression scope refers to " X is above and Y is following ". In addition, onlyWithout special instruction, the mensuration of operation and physical property etc. is all in room temperature (20～25 DEG C)/relative humidity 40～50%Condition under measure.
Next, details of the present invention is described. Can use in the present invention as composition(A) composition of main component is epoxy resin. Molecular weight easily becomes large viewpoint and considers when crosslinked, preferably existsIn a molecule, there is the compound of plural epoxy radicals. (A) composition can only use one, also canMix use two or more, if (A) composition entirety is in a liquid state at 25 DEG C, can will at 25 DEG C, be solid-stateEpoxy resin is dissolved in the epoxy resin being in a liquid state at 25 DEG C and uses. Examine from the viewpoint of storage stabilityConsider, the preferred total chlorine amount of chlorine ion concentration that can comprise in (A) composition is below 1000ppm (volume ppm),Further preferably total chlorine amount is below 700ppm. If total chlorine amount is below 1000ppm, can maintain guarantorDeposit stability.
As the object lesson of (A) composition, can illustrate by the polyatomic phenol such as epoxychloropropane and bisphenols orThe condensation of polyalcohol and the epoxy resin that obtains for example can illustrate bisphenol A-type, brominated bisphenol A type, hydrogenChange bisphenol A-type, Bisphenol F type, bisphenol S type, bisphenol A/F type, biphenyl type, naphthalene type, fluorenes type, phenolic aldehydeThe glycidols such as type, phenol phenol aldehyde type, orthoresol phenolic aldehyde type, three (hydroxyphenyl) methane type, four phenolic group ethane typesEther type epoxy. In addition, can also enumerate: by epoxychloropropane and phthalic acid derivativesOr the glycidyl ester type epoxy resin that obtains of the condensation of the carboxylic acid such as aliphatic acid; By epoxychloropropane and amine,The glycidyl amine type epoxy resin that the reaction of cyanuric acid class, hydantoins obtains; And pass through macromoleculeThe epoxy resin that the several different methods such as quantification, functional group give have been carried out modification, but be not limited in these. IfConsider performance and the viscosity of curability between low-temperature short-time, particularly preferably bisphenol A type epoxy resin or Bisphenol FType epoxy resin etc. has the epoxy resin of bis-phenol skeleton.
As commercially available epoxy resin, can enumerate: jER827,828EL that Mitsubishi chemical Co., Ltd manufacturesDeng; Japanese ink Industrial Co., Ltd manufactures greatly EPICLON (registration mark) 830, EXA-835LV etc.;Epotot (registration mark) YD-128, YDF-170 etc. that Nippon Steel & Sumitomo Metal Corporation manufactures, butBe not limited in these.
Can be poly-thiol compound as (B) composition of curing agent in the present invention. The application's polymercaptan isRefer to multi-thiol. (B) composition preferably has multiple suc as formula 1 or formula 2 such uncle mercapto or second month in a season in moleculeThe multi-thiol of mercapto. In the time having multiple mercapto, it is multi-functional thiol, thereby is cross-linked,In the time that composition solidifies, molecule quantitative change is large. Particularly, in the situation that not comprising following (E) composition, because of uncle's sulphurAlcohol radical is different on the impact of storage stability with secondary mercapto, if consider the stabilisation of storage stability,Be preferably secondary mercapto.
[Chemical formula 1]
-CH2-CH2-SH ... formula 1
As the object lesson of (B) composition, can enumerate: pentaerythrite four (3-mercaptopropionic acid ester), Ji WusiAlcohol four (3-sulfydryl butyrate), Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl acyloxy) butane, 1,3,5-tri-(3-sulfydryl butyrylOxygen base ethyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones, trimethylolpropane tris (3-sulfydryl fourthAcid esters), trimethylolethane trimethacrylate (3-sulfydryl butyrate), trimethylolpropane tris (3-sulfydryl butyrate), threeHydroxymethyl ethane three (3-sulfydryl butyrate) etc., but be not limited in these. As commodity, can enumerate:The PEMP that SC organic chemistry Co., Ltd. manufactures etc.; KarenzMT (the note that Showa Denko K. K manufacturesVolume trade mark) serial PE1, BD1, NR1 etc., but be not limited in these. Above-mentioned (B) composition can be singleSolely use one or mix use two or more.
With respect to (A) composition of 100 mass parts, (B) composition that comprises 25～95 mass parts. At (B) composition be25 mass parts when above, can reduce the viscosity of composition and show dilution effect, can remain fast simultaneouslyThe voltinism of tachy steroling. On the other hand, be below 95 mass parts time at (B) composition, can maintain storage stability. More excellentPhase selection is for (A) composition of 100 mass parts, and (B) addition of composition is 30～80 mass parts.
As (C) composition that can use in the present invention, be promote (A) composition and (B) composition react consolidateChange promoter. Curing accelerator is solid at 25 DEG C, if consider storage stability and curability,Preferably use and will there is the compound of imidazoles skeleton or addition tertiary amine stop halfway anti-on epoxy resinThe epoxy additive compound of answering is pulverized and micro mist of obtaining etc. If consider storage stability and reactivity,Be particularly preferably epoxy additive compound.
As commercially available epoxy addition compounds, can enumerate: aginomoto fine chemistry Co., Ltd. manufacturesAmicure (registration mark) series, the Fujicure (registration mark) that the TOKA of T. & K. Inc. manufacturesNovacure (registration mark) series that series or Asahi Chemical Corp manufacture etc., but not only forIn these. In addition, can also be used in combination multiple curing accelerator. Above-mentioned (C) composition can use separatelyA kind of or mixing is used two or more.
With respect to (A) composition of 100 mass parts, (C) addition of composition is preferably 1～20 mass parts. At (C)Composition is 1 mass parts when above, can show curability, is below 20 mass parts time at (C) composition, energyEnough maintain storage stability. More preferably with respect to (A) compositions of 100 mass parts, (C) addition of composition be 2～10 mass parts.
As (D) composition that can use in the present invention, except polydiorganosiloxanepolyurea, with underAny amorphous silica that has carried out chemical modification in the represented group of general formula 3～formula 5 of stating.In formula 3～formula 5, R represents respectively alkyl, preferred alkyl independently. In formula 3～formula 5 various,Adding up to more than 3 of the carbon number of R, more preferably 3～15. If the total of the carbon number of R is fewIn 3, composition cannot show sufficient shape retention. In a preferred embodiment of the present invention,In formula 3～formula 5, R represents that respectively carbon number is the alkane of 3～15 straight chain, side chain or ring-type independentlyBase. The alkyl that is 3～15 as carbon number, for example can enumerate propyl group, butyl, amyl group, hexyl,Heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, 15Alkyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl etc. Amorphous dioxy after manufactureIn SiClx, silanol (≡ SiOH) is exposed state, but by making the compound reacting with silanol in nothingSurface treatment is carried out in setting silica surface reaction (chemical modification). For example,, with the represented group of formula 6Carry out the amorphous silica of chemical modification, as long as use octyl group silane as the change of reacting with silanolCompound, carries out finishing to this amorphous silica. By adding (D) composition, can control stickyDegree or thixotropy. Powder characteristics to average grain diameter or shape etc. is not particularly limited, but considers at epoxyEasy degree and the spray nozzle clogging of the dispersion in resin, average grain diameter is preferably 0.001～50 μ m. Particularly,The amorphous silica that has most preferably carried out chemical modification with following formula 6 or the represented group of formula 7.As the object lesson of (D) composition, can enumerate the AEROSIL (note that Japanese AEROSIL Co., Ltd. manufacturesVolume trade mark) R805, RX200. Above-mentioned (D) composition can use separately one or mix and use two kindsAbove.
[Chemical formula 2]
[chemical formula 3]
With respect to (A) composition of 100 mass parts, (D) addition of composition is 5～25 mass parts. Become at (D)While dividing more than 5 mass parts, can make mobility stable, can improve operability, be less than at (D) composition simultaneouslyWhen 25 mass parts, can maintain storage stability. With respect to (A) composition of 100 mass parts, (D) compositionAddition is preferably 6～22 mass parts, more preferably 10～20 mass parts.
(E) composition that can use is in the present invention the reactive inhibitor that suppresses (C) composition. As (E)Composition, can use borate, phosphoric acid, alkyl phosphate, p-methyl benzenesulfonic acid. As borate, canEnumerate butyl borate, trimethoxy boroxin, borogen, epoxy-phenol-borate mixture (fourState changes into Industrial Co., Ltd and manufactures, cureductL-07N) etc., but be not limited in these. As alkylPhosphate, can use trimethyl phosphate, tributyl phosphate etc., but be not limited in these. (E) composition canMultiple to be used alone, but also also mix together. If consider storage stability, be preferably (E) composition and beFrom phosphoric acid, butyl borate, trimethoxy boroxin and methyl tosylate, select one withOn.
With respect to (A) composition of 100 mass parts, (E) addition of composition is preferably 0.01～5.0 mass parts.During more than 0.01 mass parts, can show storage stability at (E) composition, be less than 5.0 quality at (E) compositionWhen part, can maintain curability. More preferably with respect to (A) compositions of 100 mass parts, (E) addition of composition2～10 mass parts.
Not damaging in the scope of desired effect of the present invention, in composition epoxy resin of the present invention,In right amount the colouring agent such as hybrid pigment, dyestuff, fire retardant, plasticizer, antioxidant, defoamer,The additives such as silane coupling agent, levelling agent, rheology control agent. By adding these materials, can obtainMechanical strength of resin, bonding strength, operability, keeping quality etc. are composition and the solidfied material thereof of excellence all.
In order to maintain the shape after coating, (viscosity/height when slow speed turns the thixotropic ratio of composition epoxy resinThe viscosity in when number) be preferably 4～20, more preferably 4～15. Thus, in the present invention, can suppress to be coated withShape after cloth and expansion, after solidifying, end when coating does not also expand, and coating shape does not also becomeChange. Because composition epoxy resin of the present invention can maintain coating shape in the time being heating and curing, be therefore applicable toIn the assembling of assembling purposes, particularly camera module of electronic unit that requires accurate coating characteristics. LogicalOften, by increasing the addition as the D composition of filler, have thus that viscosity increases, thixotropic ratio is also carriedHigh trend. In addition, in this manual, " thixotropic ratio " refers to that the method that utilization is recorded in an embodiment entersThe value that row is measured.
Embodiment
Next enumerate embodiment, illustrate in greater detail the present invention, but the present invention is not limited in these enforcementExample (composition epoxy resin being only called to composition below).
[embodiment 1～10, comparative example 1～10]
For modulation group compound, prepare following compositions.
(A) composition: epoxy resin
Bisphenol f type epoxy resin (EPICLON (registration mark) EXA-835LVDIC Co., Ltd. systemMake, contained chlorine ion concentration is that 300ppm is following)
(B) composition: poly-thiol compound
Pentaerythrite four (3-mercaptopropionic acid ester) (manufacture of PEMP-20PSC organic chemistry Co., Ltd.)
Pentaerythrite four (3-sulfydryl butyrate) (the clear and electrician's strain formula meeting of KarenzMT (registration mark) PE1Society manufactures)
(C) composition: curing accelerator
Epoxy add-on type curing accelerator (Fujicure (registration mark) FXR-1081 T. & K. Inc.TOKA manufactures)
(D) composition: except polydiorganosiloxanepolyurea, carried out specific chemical modification amorphous twoSilica
Amorphous silica (AEROSIL (registration mark) R805 of the base group modification of formula 6 for powder surfaceThe manufacture of AEROSIL Co., Ltd. of Japan, average primary particle diameter are 200nm)
Amorphous silica (the AEROSIL (registration mark) of the base group modification of formula 7 for powder surfaceThe manufacture of AEROSIL Co., Ltd. of RX200 Japan, average primary particle diameter are 200nm)
(D ') composition: (D) amorphous silica outside composition
Powder surface does not carry out amorphous silica (AEROSIL (registration mark) #200 of chemical modificationAEROSIL Co., Ltd. of Japan manufactures)
Powder surface is the amorphous silica of the base group modification of methyl with the R of formula 4(AEROSIL Co., Ltd. of AEROSIL (registration mark) R972 Japan manufactures)
Powder surface has carried out the amorphous silica of chemical modification with dimethyl silicone polymer(AEROSIL Co., Ltd. of AEROSIL (registration mark) RY200 Japan manufactures)
The amorphous silica of the base group modification that powder surface is methacryloxy with the R of formula 3(AEROSIL Co., Ltd. of AEROSIL (registration mark) R7200 Japan manufactures)
(E): reaction suppressor
Phosphoric acid (reagent)
Butyl borate (reagent)
Trimethoxy boroxin (reagent)
Methyl tosylate (reagent).
Modulation embodiment 1～10 and comparative example 1～10. Weigh (A) composition, (B) composition, (D) composition to stirringMix in still, with agitator stirring 30 minutes. Afterwards, weigh (C) composition, then stir 30 minutes. Finally,Weigh (E) composition, carry out vacuum defoamation while stir 15 minutes. Detailed modulation voltage is in accordance with table 1 and table3, numerical value all represents with mass parts.
[table 1]
For embodiment 1～6, comparative example 1～8, carry out viscosimetric analysis (initial stage), shape retention confirmation,The confirmation that the confirmation of storage stability, the confirmation of curability, siloxanes contain, it the results are summarized in table 2.
[viscosimetric analysis (initial stage)]
According to following condition determination, use the cone-template rotation that by circulation thermostat, cup is adjusted to 25 DEG CViscosimeter (E type viscosimeter). Cone uses 3 ° × R12 type. Gather 0.5cc composition, be expressed into specimen cupCentral part. Specimen cup is arranged on body, carries out the mensuration of 3 minutes. Measure the rotation speed of 2.5rpmThe rotary speed of degree and 25.0rpm, and respectively as " initial stage viscosity 1 (mPas) ", " initial stage viscosity 2 (mPas) ".In addition, using the calculated value of viscosity 1/ viscosity 2 as " thixotropic ratio ". High and exceeded viscosity type in viscosityWhen measurement range, be denoted as "-", cannot calculate thixotropic ratio time, be also denoted as "-". If consider while extruding and occurThe bad situation such as wire drawing, viscosity 1 is preferably 10～200mPas, viscosity 2 is preferably 1～30mPas.In addition, if the mobility of considering, preferably thixotropic ratio is 4～20.
[confirmation of shape retention]
0.1g composition is expressed on glass plate, takes the photo of the shape while extruding, simultaneously from being coated withRise the opposition side of one side of composition, marks in the end during to coating. Afterwards, glass plate is being tiltedUnder the state of 45 °, place 10 minutes under 80 DEG C of environment. Shape and photo after placing are compared,Confirm the end position after placing simultaneously, confirm " shape retention " by following metewand. For canCarry out precision coating, be preferably "○".
Metewand
Zero: end when coating does not expand, and shape does not also change;
△: end when coating does not expand, but variation has occurred shape;
×: end expanding when coating.
[confirmation of storage stability]
After modulation group compound, be kept in container, under the environment of 25 DEG C, placed 7 days. Afterwards, will holdDevice Kaifeng, evaluates " storage stability " according to following metewand. As storage stability of the present invention,Be preferably "○".
Metewand
Zero: gelation does not occur, there is mobility;
×: there is gelation, there is no mobility.
[confirmation of curability]
0.1g composition is dripped on the hot plate that is set as 80 DEG C, the rod of top point is contacted with composition,Use timer measure until composition become do not have sticking state, i.e. curing time. According to followingMetewand is evaluated " curability ". Curability of the present invention was preferably in 6 minutes.
Metewand
In zero: 6 minute;
×: exceed 6 minutes.
[confirmation of siloxanes]
Use gas chromatography mass spectrometer (so-called GC-MS), carried out low-molecular-weight annular siloxane((SiO(CH3)2)n, n=3～20) qualitative analysis. (D) composition or (D ') are become to be distributed in aluminium cup, arrangeIn the upper space of GC-MS, at 85 DEG C, heat 3 hours, extract out degassedly, pass through gas chromatographSeparate various degassed compositions. According to following metewand, evaluate and whether confirmed low-molecular-weight ring-typeThe fragment of siloxanes, and be denoted as " siloxanes ". In the present invention, preferably do not produce low-molecular-weight ring-type siliconOxygen alkane.
Metewand
Zero: do not produce low-molecular-weight annular siloxane;
×: produce low-molecular-weight annular siloxane.
[table 2]
When embodiment 1～6 is compared with comparative example 1,2 and 4, (D) in composition, only has specific compositionCan show shape retention. In addition, when embodiment 1～6 is compared with comparative example 5～7, phaseFor (A) composition of 100 mass parts, (B) composition can have shape guarantor concurrently in the scope of 25～95 mass partsHolding property and curability. In comparative example 5, (B) addition of composition is very few, and the dilution effect of composition is low,It is very high that viscosity becomes, and adds and be difficult to man-hour extrude. In addition, in comparative example 6 and 7, (B) composition is too much,Be not cured on the contrary, shape retention or curability decline. By embodiment 1～6 and comparative example 8More known: with respect to (A) composition of 100 mass parts, thereby (D) composition is that 5～25 mass parts have maintained shapeShape retentivity. In comparative example 3, although thixotropic ratio is high, because (D ') composition has produced low-molecular-weight ring-typeSiloxanes, is not therefore suitable for electronic unit.
[table 3]
For embodiment 7～10, comparative example 9,10, viscosimetric analysis (after keeping), shape retention are carried outConfirmation, the confirmation of curability, the confirmation of siloxanes, it the results are summarized in table 4.
[viscosimetric analysis (after keeping)]
After modulation group compound, it is carried out to above-mentioned viscosimetric analysis, afterwards, under the environment of 25 DEG C, places 7 days,Again carry out viscosimetric analysis according to the method identical with the mensuration of initial stage viscosity. Using result now as " protectingViscosity 1 (mPas) after pipe ", " keeping after viscosity 2 (mPas) ", " thixotropic ratio after keeping ". Rate of change is that use (is protectedAfter pipe-and initial stage) value that calculates of/initial stage × 100 is as " rate of change (%) ". Rate of change is preferably-50%～+ 50%, more preferably-10%～+ 10%. Rate of change in ± 50% scope time, for example, utilizes noteWhen emitter is pressurizeed with certain pressure, viscosity is difficult to change, and coating weight is stable. In addition, also canIn the time being coated with, be difficult to the advantages such as wire drawing to list. The composition that viscosity has been exceeded to measurement range is denoted as "-".In addition, rate of change now is also denoted as "-".
[table 4]
When embodiment 1,7～10 is compared with comparative example 9,10, by using (E) composition, can fallLow rate of change. In addition, even in embodiment 7～10, shape retention, curability have also been maintained, alsoDo not produce low-molecular-weight annular siloxane.
Practicality in industry
Shape can maintain coating due to composition epoxy resin of the present invention in the time being heating and curing time, thereforeCan realize accurate coating characteristics, due to can low-temperature setting, so its harmful effect to electronic unitAlso lack, and can be used in all purposes of the assembling of electronic unit.
Claims (8)
1. a composition epoxy resin, described composition epoxy resin comprises (A)～(E) composition, and relativelyIn (A) of 100 mass parts composition, (B) composition that comprises 25～95 mass parts, (C) of 1～20 mass parts becomePoint, (D) composition of 5～25 mass parts and (E) composition of 0.01～5 mass parts,
(A) composition is epoxy resin;
(B) composition is poly-thiol compound;
(C) composition is curing accelerator;
(D) composition be except polydiorganosiloxanepolyurea, show by any in following general formula 3～5The group showing has carried out the amorphous silica of chemical modification,
[Chemical formula 1]
Wherein, R represents respectively alkyl independently, the carbon number of the R in general formula 3～5 various totalMeter is more than 3;
(E) composition is reaction suppressor.
2. composition epoxy resin according to claim 1, wherein, thixotropic ratio is more than 4.0.
3. composition epoxy resin according to claim 1 and 2, wherein, described (C) composition is epoxyAdditive compound.
4. composition epoxy resin according to claim 1 and 2, wherein, described (E) composition is from phosphorusAt least one that select in acid, butyl borate, trimethoxy boroxin and methyl tosylate.
5. composition epoxy resin according to claim 1 and 2, wherein, described (D) composition be exceptOutside polydiorganosiloxanepolyurea, carried out chemical modification with following formula 6 or the represented group of formula 7Amorphous silica,
[Chemical formula 2]
6. composition epoxy resin according to claim 1 and 2, wherein, described (A) composition is to haveThe epoxy resin of bis-phenol skeleton.
7. composition epoxy resin according to claim 1 and 2, wherein, described (B) composition is to divideIn son, there is the poly-thiol compound of the functional group of plural following formula 2,
[chemical formula 3]
8. composition epoxy resin according to claim 1 and 2, wherein, described epoxy resin combinationThing is for the assembling of camera module.
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| JP2014-229500 | 2014-11-12 |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR102359684B1 (en) | 2022-02-07 |
| JP6849899B2 (en) | 2021-03-31 |
| KR20160056784A (en) | 2016-05-20 |
| CN105585937B (en) | 2020-01-03 |
| JP2016102206A (en) | 2016-06-02 |
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