CN100518939C - Anion exchanger and resin composition for electronic part sealing utilizing the same - Google Patents
Anion exchanger and resin composition for electronic part sealing utilizing the same Download PDFInfo
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- CN100518939C CN100518939C CNB2004800446464A CN200480044646A CN100518939C CN 100518939 C CN100518939 C CN 100518939C CN B2004800446464 A CNB2004800446464 A CN B2004800446464A CN 200480044646 A CN200480044646 A CN 200480044646A CN 100518939 C CN100518939 C CN 100518939C
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- anion exchanger
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/10—Inorganic material
Abstract
The present invention provides an anion exchanger which realizes exhibiting of low moisture absorption and/or excelling in heat resistance, and further excels in anion exchange performance in the vicinity of neutrality; and a resin composition for electronic parts and electrical parts utilizing the same. Further, the present invention provides an electronic part or electrical part including the resin composition and a product including the same. In particular, there is provided an anion exchanger comprising a specified hydrotalcite sintering product and/or specified hydrotalcite compound having been treated with a metal salt solution and/or metal alkoxide solution. Furthermore, there is provided an anion exchanger comprising a specified hydrotalcite compound sintering product and metal alkoxide solution and/or a bivalent metal oxide having been treated with a metal salt solution.
Description
Technical field
The present invention relates to a kind of calcined material with hydrotalcite (hydrotalcite) compound of good anion exchange.In addition, also relate to a kind of resin composition for electronic part sealing with superior in reliability of this hydrotalcite calcined material and solidfied material of said composition of using.
Background technology
As everyone knows, hydrotalcite has anion exchange, can adsorb to belong to anionic chloride ion etc., utilizes this function, and hydrotalcite can be widely used in fields such as pharmaceuticals, fire retardant, electronic material.
LSI, IC, mixing IC, transistor, diode, IGCT and these mixing part, great majority are to use epoxy resin to encapsulate.These electron device package materials can suppress raw material intermediate ion impurity except needs or the caused bad situation of the moisture of invading from the outside time, also need to possess electrical characteristics such as anti-flammability, high-adhesiveness, crack resistance and high specific volume resistance etc. and plant specific character.
Be widely used as in the epoxy resin of electron device package material, except epoxy resin compound, also contain epoxide curing agent, curing accelerator, inorganic filler, fire retardant, pigment and organosilan coupling agent etc. as principal component.
And then in recent years along with semi-conductive highly integrated, the aluminium wiring width on the IC wafer diminishes gradually, has caused taking place ahead of time of aluminium corrosion thus.This corrosion mainly is to invade in facilitating as the moisture in the epoxy resin of encapsulation material.In addition, because dwindling of wiring width, the heat that has caused taking place in the use increases, and therefore need allocate a large amount of fire retardants such as antimony oxide, brominated epoxy resin and inorganic hydroxide in this epoxy resin, and these fire retardants become branch further to promote the corrosion of wirings such as aluminium.
In order to prevent above-mentioned corrosion, need further to improve the moisture-proof reliability of epoxy resin.Improve the demand of moisture-proof reliability aspect at this, existing people has proposed in epoxy resin etc. that allotment is a kind of to belong to inorganic anion exchanger composed hydrotalcite, with seizure become the foreign ion of problem, the particularly scheme of halogen ion (reference example such as spy open clear 63-252451 communique, spy open clear 64-64243 communique, and the spy open clear 60-40124 communique etc.)
Hydrotalcite compound is the lamellar compound that is shown below,
M
2+ aM
3+ b(OH
-)
c(A
n-)d·mH
2O
(M
2+Expression divalent metal, M
3+Be 3 valency metals, A
N-Be the anion of n valency, a, b, c, d and m are positive number).
Particularly, Mg is arranged usually
4.5Al
2(OH)
13CO
33.5H
2O, Mg
4.3Al
2(OH)
12.6CO
33.5H
2O, Mg
6Al
2(OH)
16CO
34H
2The magnalium hydrotalcite that composition formulas such as O are represented.Because this compound has had anion such as hydroxyl ion and carbonic acid ion, not talkative have enough anion exchange performances.
By calcining this hydrotalcite compound, anion in its structure is broken away from and become the represented material of following formula,
M
2+ xM
3+ yO
z
(M
2+Expression divalent metal, M
3+Be that 3 valency metals, x, y and z are positive number).
This hydrotalcite calcined material is not because contain anion in the compound, so compare with hydrotalcite, it has more excellent anionic switching performance.This hydrotalcite calcined material can become layer structure after absorbing water once more.
Also the someone has proposed the scheme (for example opening clear 60-42418 communique with reference to the spy) of this hydrotalcite calcined material of allotment in epoxy resin etc.This hydrotalcite calcined material has the excellent anionic switching performance, can promote the moisture-proof reliability of electronic device effectively, but because its hygroscopicity is very high, also moisture absorption easily in air is so exist the moisture absorption in the electronic device and follow the volume of moisture absorption to increase problem.Therefore, when it is exposed to high temperature in solder bath, counter-current welding equipment processing etc., because of the different thermal stress that produce such as the thermal coefficient of expansion of substrate etc., institute's hygroscopic moisture might cause peeling off at embeddings product such as element, guiding frame and between encapsulating with moulding material through the vapour pressure that gasification produces, become the reason that encapsulates be full of cracks, damage to wafers etc.
In addition, generally speaking anion exchanger when environment on every side is relatively acid, is easier to adsorpting anion; If near neutral or when relatively alkaline, then more difficult adsorpting anion, and modulated is assigned in the influence of the additive of encapsulation material, and the pH of resin combination sometimes can be near neutrality, and can't bring into play the effect of anion exchanger this moment fully.
Be directed to this, the someone has proposed to mix the cation exchange column that belongs to solid acid and has reduced apparent pH in anion exchanger, and promotes the method for using after the ion exchangeable (for example opening clear 60-23901 communique with reference to the spy) thus.But, when in resin, adding solid acid, can damage the rerum natura of resin.In addition, many cation exchange columns contain heavy metal, and recently because consider environmental problem, can't and use cation exchange column sometimes.
The known material (for example opening flat 05-140419 communique) of allocating inorganic ion exchangers such as cation exchange column, anion exchanger and amphion permutoid at the epoxy resin that is used for printed wiring board with reference to the spy.
In addition, make aromatic polyamide fibre contain epoxy resin or the printed base plate of polyphenylene oxide resin and ion capturing agent also is known.Can enumerate ion exchange resin and inorganic ion exchanger as this ion capturing agent, as inorganic ion exchanger, the mentioned material that antimony-bismuth system is arranged and the material (for example opening flat 09-314758 communique) of zirconium system with reference to the spy.
The ion capturing agent that contains insulating varnish is known, uses this insulating varnish can make multilayer printed-wiring board.Can enumerate (for example opening flat 10-287830 communique) such as activated carbon, zeolite, silica gel, activated alumina, atlapulgite, hydration antimony pentaoxide, basic zirconium phosphate and hydrotalcites as this ion capturing agent with reference to the spy.
In addition, the material at the adhesive-film allotment inorganic ions adsorbent that is used for multiwiring board also is known.Can enumerate (for example opening flat 10-330696 communique) such as activated carbon, zeolite, silica gel, activated alumina, atlapulgite, hydration antimony pentaoxide, basic zirconium phosphate and hydrotalcites as this inorganic ions adsorbent with reference to the spy.
In addition, the epoxy resin adhesive that contains ion capturing agent is known, can enumerate anion exchanger or cation exchange column (for example opening flat 10-013011 communique with reference to the spy) as this ion capturing agent.
Also have, the conductive epoxy cream that contains ion capturing agent and silver powder etc. is known.Can enumerate (for example opening flat 10-007763 communique) such as nitric hydrate bismuth, magnalium hydrotalcite, antimony oxides as this ion capturing agent with reference to the spy.
Among the ion exchanger ion capturing agent of mentioning, the example that uses hydrotalcite is also arranged in the above, and be that use directly use or calcining back in these examples.
Summary of the invention
The object of the present invention is to provide a kind of anion exchanger, its hygroscopicity is little and have a good hear resistance, and near neutrality, have the excellent anionic exchangeability, the resin combination that provides its used for electronic device of use and electric component to use is provided.In addition, another purpose is electronic device, the electric component that uses this resin combination to be provided and to use their goods.
The inventor finds after deliberation, following anion exchanger can solve above-mentioned problem, thereby finished the present invention, described anion exchanger is, by using hydrotalcite calcined material shown in metal salt solution and/or the metal alkoxide solution processing following formula (1) and/or the hydrotalcite compound shown in the following formula (2) to obtain
M
2+ xM
3+ yO
z (1)
The M of formula (1)
2+Be Mg
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, or Zn
2+, M
3+Be Al
3+, Fe
3+, Cr
3+, Co
3+, or In
3+, x, y, z are positive number, the 2x+3y=2z more than 0.1, and x〉and the value of y, x/y is below 9.
M
2+ 1-x M
3+ x(OH
-)
2(A
n-)
d·mH
2O (2)
The M of formula (2)
2+Be Mg
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, or Zn
2+, M
3+Be Al
3+, Fe
3+, Cr
3+, Co
3+, or In
3+, A
N-Be OH
-, F
-, Cl
-, Br
-, NO
3 -, CO
3 2-, SO
4 2-, Fe (CN)
6 3-, CH
3COO
-, oxalic ion or salicylic acid ion the anion of n valency, X is the positive number below 0.33 more than 0.1, m is 0 or positive number, d is X/n.
Anion exchanger of the present invention is, uses above-mentioned metal salt solution and metal alkoxide solution to handle the anion exchanger that forms, described metal for by silicon, titanium, zirconium, tin, and aluminium in select more than at least a kind.
The present invention relates to a kind of anion exchanger, it cooperates the divalent metal oxide to form in above-mentioned anion exchanger again.
In addition, another form of the present invention is a kind of anion exchanger, and it contains the calcined material and the divalent metal oxide of the hydrotalcite compound shown in the formula (2).Relate to and use metal salt solution and/or metal alkoxide solution to handle the anion exchanger that this anion exchanger forms.
M
2+ 1-x M
3+ x(OH
-)
2(A
n-)
d·mH
2O (2)
The M of formula (2)
2+Be Mg
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, or Zn
2+, M
3+Be Al
3+, Fe
3+, Cr
3+, Co
3+, or In
3+, An
-Be OH
-, F
-, Cl
-, Br
-, NO
3 -, CO
3 2-, SO
4 2-, Fe (CN)
6 3-, CH
3COO
-, oxalic ion or salicylic acid ion the anion of n valency, X is the positive number below 0.33 more than 0.1, m is 0 or positive number, d is X/n.
Anion exchanger of the present invention is, uses above-mentioned metal salt solution and metal alkoxide solution to handle the anion exchanger that forms, described metal for by silicon, titanium, zirconium, tin, and aluminium in select more than at least a kind.
Another form of the present invention is a kind of resin composition for electronic part sealing, wherein contains above-mentioned anion exchanger, at this moment, also can contain the inorganic cation permutoid.
Another form of the present invention is solidified the used for sealing electronic device resin that forms for making this resin composition for electronic part sealing.
Another form of the present invention is a kind of electronic device, is to use this resin composition for electronic part sealing potted element to form.
Another form of the present invention for a kind of varnish (varnish), bonding agent or cream, wherein contains above-mentioned anion exchanger, also can contain the inorganic cation permutoid.
Another form of the present invention is a kind of goods, contains above-mentioned varnish, bonding agent or cream.
Description of drawings
Fig. 1 is hydrotalcite compound Mg
4.5Al
2(OH)
13CO
33.5H
2The result of the thermal mass assay determination (TG-DTA) of O (MAH1), transverse axis is represented temperature ℃, and the left longitudinal axis is represented slip, and the right longitudinal axis is represented the arbitrary value among the differential curve b of hot decrement curve a, and a represents hot decrement curve, b represents the differential curve of hot decrement curve a.
Fig. 2 is the X-ray diffraction figure of anion exchanger A-2.
Fig. 3 is the X-ray diffraction figure of anion exchanger A-4.
Fig. 4 is in the X-ray diffraction figure of 550 ℃ of materials (tMAH1) of forming of calcining MAH1.
Fig. 5 is the X-ray diffraction figure of MAH1.
Among Fig. 2-5, transverse axis is the angle of diffraction (2 θ) in the X-ray diffraction, and the longitudinal axis is the diffracted intensity value in the X-ray diffraction.
The specific embodiment
Below describe the present invention in detail.
Among the present invention, use metal salt solution and/or metal alkoxide solution to handle hydrotalcite calcined material shown in the following formula (1) and/or the hydrotalcite compound shown in the following formula (2), so-called " processing " calcined after being meant and giving slaine and/or metal alkoxide in the mode of wet type or dry type.
M
2+ xM
3+ yO
z (1)
The M of formula (1)
2+Be Mg
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, or Zn
2+, M
3+Be Al
3+, Fe
3+, Cr
3+, Co
3+, or In
3+, x, y, z are positive number, the 2x+3y=2z more than 0.1, and x〉and the value of y, x/y is below 9.
M
2+ 1-xM
3+ x(OH
-)
2(A
n-)
d·mH
2O (2)
The M of formula (2)
2+Be Mg
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, or Zn
2+, M
3+Be Al
3+, Fe
3+, Cr
3+, Co
3+, or In
3+, An
-Be OH
-, F
-, Cl
-, Br
-, NO
3 -, CO
3 2-, SO
4 2-, Fe (CN)
6 3-, CH
3COO
-, oxalic ion or salicylic acid ion the anion of n valency, X is the positive number below 0.33 more than 0.1, m is 0 or positive number, d is X/n.
Hydrotalcite compound shown in hydrotalcite calcined material shown in the formula (1) and/or the formula (2) is called hydrotalcite-based compound.
Zero hydrotalcite-based compound
Hydrotalcite calcined material used in the present invention is the material shown in the following formula (1).
M as formula (1)
2+Can enumerate magnesium, manganese, iron, cobalt, nickel, copper, zinc etc., with magnesium, zinc, nickel, and cobalt be good, serve as special good with magnesium, zinc.
The M of formula (1)
3+Can enumerate aluminium, iron, chromium, cobalt, indium etc., be good with aluminium, iron, cobalt, is special good with aluminium.
The x/y value of formula (1) is below 9, being good below 7, with below 6 for better.In addition, the x/y value is more than 2, being good more than 2.1, with more than 2.2 for better.
Hydrotalcite calcined material used in the present invention can obtain by the hydrotalcite compound shown in the calcining following formula (2).Hydrotalcite compound used in the present invention is so long as the hydrotalcite compound shown in the formula (2) gets final product, and there is no particular limitation.
M as formula (2)
2+Can enumerate magnesium, manganese, iron, cobalt, nickel, copper, zinc etc., with magnesium, zinc, nickel, and cobalt be good, serve as special good with magnesium, zinc.
M as formula (2)
3+Can enumerate aluminium, iron, chromium, cobalt, indium etc., be good with aluminium, iron, cobalt, is special good with aluminium.
The X of formula (2) is more than 0.1 below 0.33, and X to be being good more than 0.125, being preferable more than 0.143, with more than 0.16 for better, serving as special good more than 0.2; Being good below 0.32, with below 0.31 for better.
The A of formula (2)
N-Be OH
-, F
-, Cl
-, Br
-, NO
3-, CO
3 2-, SO
4 2-, Fe (CN)
6 3-, CH
3COO
-, oxalic ion or salicylic acid ion the anion of n valency, can removedly being good through calcining.The A of formula (2)
N-Specifically with OH
-, NO
3 -, CO
3 2-, CH
3COO
-, oxalic ion or salicylic acid ion be good, with OH
-, NO
3 -, or CO
3 2-For better, with CO
3 2-For the spy good.
The temperature of the hydrotalcite compound shown in the calcining formula (2) is not particularly limited, for removing the anionic temperature in the hydrotalcite compound.In addition, this calcining heat is for example 240～1000 ℃, the X value of factor (2) and different.
Calcination time can be set the optimal time according to kind, calcining heat and the calcining amount of hydrotalcite.For example, calcination time to be being good below 24 hours, being preferable below 15 hours, with below 10 hours for better; Being good more than 0.5 hour.
With the X of formula (2) is material more than 0.29, more than 240 ℃ and be lower than the calcined material that 700 ℃ temperature lower calcination forms, because near the anion exchange performance neutral is not good, is necessary to be used with the divalent metal oxide.The calcining heat of this calcined material to be being good more than 330 ℃, being preferable more than 400 ℃, with more than 430 ℃ for better, serving as special good more than 500 ℃.When calcining heat is hanged down, because anion can't be removed from hydrotalcite compound, the situation that ion exchangeable reduces appears sometimes, and therefore not ideal.
With the X of formula (2) is material more than 0.29, and the calcined material in that calcining forms below 1000 ℃ more than 700 ℃ can generate the divalent metal oxide.In the calcined material of this moment, also can not add the divalent metal oxide.This calcined material is good near the anion exchange performance neutral, mismatch the divalent metal oxide also can, if cooperation is then better.The calcining heat of this calcined material, being preferable below 900 ℃, with below 850 ℃ for better.Calcining heat Ruo Taigao causes anion exchanger to decompose sometimes, causes ion exchange capacity to reduce, and is therefore undesirable.
The X of formula (2) is lower than 0.29 material, and the calcined material in that calcining forms below 1000 ℃ more than 240 ℃ can generate the divalent metal oxide.The calcined material of this moment also can not added the divalent metal oxide.This calcined material is good near the anion exchange performance neutral, do not allocate the divalent metal oxide also can, if allocate then better.In addition, the X value too hour can appear near the situation of the anion exchange degradation neutral.The calcining heat of this calcined material is good with 330～1000 ℃, is preferable with 400～950 ℃, with 430～950 ℃ for better, serve as special good with 500～900 ℃.When this calcining heat is hanged down, because of anion being removed from hydrotalcite compound, the situation that ion exchangeable reduces can appear.On the contrary, when calcining heat is too high, can cause ion exchanger to decompose, cause ion exchange capacity to reduce, therefore undesirable.
Whether the divalent metal oxide is created in the calcined material of hydrotalcite compound, can investigate by X-ray diffraction.
Be specially, for example M
2+Be Mg
2+The time, with the standard items of X-ray diffraction mensuration MgO, compare by angle of diffraction (2 θ) afterwards earlier with calcined material, can confirm the generation of MgO.
Hydrotalcite compound shown in the formula (2) is only calcined in the material that forms, and its chlorion exchange rate is with greater than 70% being good, being preferable more than 80%, with more than 90% for better.
In addition, the chlorion exchange rate is, the material that the hydrotalcite compound shown in the calcining formula (2) of a gram is formed, the value that the amount of chloride ions when handling with the sodium-chloride water solution 50ml of 0.02 molar concentration is calculated.
With regard to the anion exchanger of the present invention or the hygroscopicity of anion exchange composition, the weight increase place 24 hours in 35 ℃, the environment of relative humidity 90% after to be being good below 50%, being preferable below 40%, with below 20% for better.
In addition, during with the chlorion exchange rate of anion exchanger of the present invention and hygroscopicity combination evaluation, its weight increase greater than the situation below 40% and 50% under, the chlorion exchange rate to be being good more than 80%, with more than 90% for better.Weight increase is 40% when following, and the chlorion exchange rate to be being good more than 65%, being preferable more than 70%, with more than 80% for better, serving as special good more than 90%.
As hydrotalcite compound, can enumerate Mg
4.5Al
2(OH)
13CO
33.5H
2O, Zn
4.5Al
2(OH)
13CO
33.5H
2O, Ni
4.5Al
2(OH)
13CO
33.5H
2O, Mg
4.5Fe
2(OH)
13CO
33.5H
2O, Mg
5Al
1.5(OH)
13CO
33.5H
2O, Mg
6Al
2(OH)
16CO
34H
2O or with magnesium and aluminium with the synthetic material of mol ratios such as 2.5:1,2.75:1,4:1,5:1.In addition, can enumerate Mg0 as these calcined material
7Al
0.3O
1.15, Zn
0.7Al
0.3O
1.15, Ni
0.7Al
0.3O
1.15, Mg
0.7Fe
0.3O
1.15, Mg
0.8Al
0.24O
1.16, Mg
0.9Al
0.3O
1.35, Mg
2.5AlO
4, Mg
2.75AlO
4.25, Mg0
8Al
0.24O
1.16, Mg
1.2AlO
2.7, Mg
1.5AlO
3.0, Mg
3AlO
4.5, Mg
4AlO
5.5, Mg
5AlO
6.5Deng.
Zero metal salt solution and metal alkoxide solution
As the metal salt solution of handling hydrotalcite-based compound and the metal of metal alkoxide solution, be good with silicon, titanium, zirconium, tin and aluminium etc., with silicon, titanium, zirconium, and aluminium for better, serve as that the spy is good with silicon and titanium.
There is no particular limitation to handle the method for hydrotalcite-based compound with metal salt solution and/or metal alkoxide solution.Following processing method is for example arranged.
Hydrotalcite-based compound is disperseed in metal salt solution, filter, clean, dry, calcining method.
Hydrotalcite-based compound is disperseed in metal salt solution, add alkaline matters such as NaOH, ammoniacal liquor, behind the surperficial precipitating metal oxide or metal hydroxides of hydrotalcite-based compound, filter, clean, drying, calcining method.
Hydrotalcite-based compound is disperseed in metal salt solution, add amines such as urea, six methylene tetramines,, behind the surperficial precipitating metal oxide or metal hydroxides of hydrotalcite-based compound, filter, clean, drying, calcining method by heating.
Hydrotalcite-based compound is disperseed in metal alkoxide solution, make the metal alkoxide hydrolysis by adding acid, alkali or water or heating, behind the surperficial precipitating metal oxide or metal hydroxides of hydrotalcite-based compound, filter, clean, dry, calcining method.
Add metal alkoxide or metal alkoxide solution in hydrotalcite-based compound, mix the back heating, surface-coated metal oxide or metal hydroxides at hydrotalcite-based compound carry out drying, calcining method.
By using metal salt solution and/or being that metal alkoxide solution is handled hydrotalcite-based compound, can obtain the less anion exchanger of hygroscopicity, preferable.
If will use anion exchanger of the present invention in resin composition for electronic part sealing, person is not good not contain the ionic impurity as far as possible for it.When using metal salt solution to handle hydrotalcite-based compound, must clean fully and remove this salt.On the other hand, when using metal alkoxide solution to handle, because there is not or has only a spot of by-product salt, so be better than metal salt solution.
The metal of metal salt solution such as above-mentioned, this metal salt solution can be the aqueous solution or sol solution.Can enumerate alkali metal salt, halide of the oxyacid of silicon, titanium, zirconium, tin or aluminium etc. as this slaine.Alkali metal salt is good with sodium salt or sylvite, and halide is good with chloride or bromide.
The metal of metal alkoxide such as above-mentioned.Can enumerate the aqueous solution, moisture alcoholic solution and alcoholic solution etc. as the solution of metal alkoxide solution, be good with moisture alcoholic solution or alcoholic solution.
Concrete example as metal alkoxide, can enumerate tetraethoxysilane, tetramethoxy-silicane, four different third titanium oxide, three ethoxyquin aluminium, four different third zirconias, tin tetraethoxide, tetramethoxy tin and their polymer (for example methyl silicate oligomer, ethyl orthosilicate oligomer, positive silicic acid propyl ester oligomer etc.) because tetraethoxysilane, tetramethoxy-silicane, and their hydrolysis rate of polymer can not handle too soon and easily and preferable.With the polymer of tetraethoxysilane, the polymer of tetramethoxy-silicane etc. for better.
Using metal salt solution and/or metal alkoxide solution to come the calcining heat of the material that the hydrotalcite calcined material shown in hybrid (1) forms, be good with 50～1000 ℃, is preferable with 100～900 ℃, with 200～800 ℃ for better, serve as that the spy is good with 400～700 ℃.
Using metal salt solution and/or metal alkoxide solution to come the calcining heat of the material that the hydrotalcite compound shown in hybrid (2) forms, be good with 400～1000 ℃, with 500～900 ℃ for better, serve as that the spy is good with 500～700 ℃.
Also can use metal salt solution and/or metal alkoxide solution, exchange the composition that water distribution talcs compound and divalent metal oxide form and handle, these treatment conditions are with above-mentioned identical.
The processing of using metal salt solution and/or metal alkoxide solution to carry out is considered near the anion exchange performance neutrality, to carry out to good before allotment divalent metal oxide.
The processing ratio of zero metal salt solution or metal alkoxide solution
With respect to the metal salt solution of hydrotalcite-based compound and/or be that the processing ratio of metal alkoxide solution is not particularly limited, preferable ratio is with respect to hydrotalcite-based compound 100 weight portions, metal salt solution and/or be that metal oxide (metal salt solution or the metal of metal alkoxide solution are converted into oxide to form) in the metal alkoxide solution is 3～100 weight portions serves as special good with 5～50 weight portions.When metal oxide is less than 3 weight portions, can occur suppressing hygroscopic situation, and, if it is not greater than 100 weight portions, good because situation that ion exchange capacity diminishes can occur.
Zero divalent metal oxide
The metal of divalent metal oxide used in the present invention is with Mg
2+, Mn
2+, Fe
2+, Co
2+, Cu
2+, Zn
2+On the divalent metal is good, more preferably with hydrotalcite-based compound in the oxide of divalent metal same metal.
The particle diameter of divalent metal oxide is not particularly limited, and average grain diameter is to be good below the 10 μ m more than the 0.01 μ m, more preferably below the above 3 μ m of 0.05 μ m.Particle diameter is that 0.01 μ m condenses when following easily, when 10 μ m are above, damages rerum natura sometimes when being added in the resin and not good.
The allotment ratio of zero divalent metal oxide
Allotment ratio for hydrotalcite-based compound and divalent metal oxide is not particularly limited.
Use metal salt solution and/or be metal alkoxide solution when handling material that hydrotalcite-based compound forms and being 100 weight portions, the divalent metal oxide is good with 10～500 weight portions, for better, serves as that spy good with 40～100 weight portions with 20～200 weight portions.When this divalent metal oxide is less than 10 weight portions, have the situation that ion exchangeable can't promote; During greater than 500 weight portions, not good because ion exchange capacity diminishes.
With the X in the formula (2) at the material more than 0.29, more than 240 ℃, when being lower than calcined material that 700 ℃ temperature calcining forms and being 100 weight portions, the divalent metal oxide is good with 10～1000 weight portions, is preferable with 20～300 weight portions, with 40～200 weight portions for better.With respect to this calcined material, the divalent metal oxide has the situation that ion exchangeable can't promote if be less than 10 weight portions; During more than 1000 weight portions, not good because ion exchange capacity diminishes.
At the material more than 0.29,, when near the anion exchange performance neutral is not good, can make it contain the divalent metal oxide X in the formula (2) in the calcined material that calcining forms below 1000 ℃ more than 700 ℃.This moment, the divalent metal oxide was good with 10～500 weight portions, is preferable with 20～200 weight portions with respect to these calcined material 100 weight portions, served as special good with 40～100 weight portions.With respect to this calcined material, the divalent metal oxide has the situation that ion exchangeable can't promote if be less than 10 weight portions; During more than 500 weight portions, not good because ion exchange capacity diminishes.
X in the formula (2) is lower than material below 0.29,, when near the anion exchange performance neutral is not good, can makes it contain the divalent metal oxide in the calcined material that calcining forms below 1000 ℃ more than 240 ℃.This moment is with respect to these calcined material 100 weight portions,, the divalent metal oxide is good with 10～500 weight portions, is preferable with 20～200 weight portions, serves as special good with 40～100 weight portions.With respect to this calcined material, the divalent metal oxide has the situation that ion exchangeable can't promote if be less than 10 weight portions; During more than 500 weight portions, not good because ion exchange capacity diminishes.
Zero resin composition for electronic part sealing
As the resin that in the resin composition for electronic part sealing that cooperates anion exchanger of the present invention, uses, can use phenolic resins, Lauxite, melmac, unsaturated polyester resin, and heat-curing resin such as epoxy resin, also can use thermoplastic resins such as polyethylene, polystyrene, polyvinyl chloride and polypropylene, be good to use heat-curing resin.As employed heat-curing resin in the resin composition for electronic part sealing of the present invention, be good with phenolic resins or epoxy resin, be special good with epoxy resin.
Zero used for sealing electronic device composition epoxy resin
Epoxy resin used in the present invention, so long as can get final product as the used for sealing electronic device resin, unqualified.For example if having 2 above epoxy radicals in 1 molecule, can solidify can and no matter its kind, for example phenol-novolac type epoxy resin, bisphenol A type epoxy resin, cycloaliphatic epoxy resin etc. can all can use as moulding material.In addition, in order to promote the moisture-proof of composition of the present invention, as epoxy resin preferably use chloride ion content as below the 10ppm and water-disintegrable chlorinity be the material below the 1000ppm.
Used for electronic device composition epoxy resin of the present invention is good to contain curing agent and curing accelerator.
As employed curing agent among the present invention, known can be as can the using of the curing agent of composition epoxy resin, it is that curing agent and novolaks are curing agent etc. that preferable concrete example has acid anhydrides, amine.
As employed curing accelerator among the present invention, known can be as can the using of the curing accelerator of composition epoxy resin, preferable concrete example has amine system, phosphorus system, and the promoter of imidazoles system.
Resin composition for electronic part sealing of the present invention can be allocated the known material that can allocate in case of necessity in molding resin.Can enumerate inorganic filler, fire retardant, inorganic filler coupling agent, colouring agent, reach releasing agent etc. as this composition.These compositions can use the known composition that can allocate in epoxy resin in moulding.The preferred embodiment of inorganic filler, adducible have crystallinity silicon dioxide powder, fused silica powder, fused silica powder, alumina powder and a talcum etc., wherein with crystallinity silicon dioxide powder, fused silica powder, and the fused silica powder because cheap and preferable.The example of fire retardant has antimony oxide, halogenated epoxy resin, magnesium hydroxide, aluminium hydroxide, red phosphorus based compound, phosphate based compound etc., the example of coupling agent has silane system and titanium system etc., and the example of releasing agent has waxes such as aliphatic paraffin, senior aliphat alcohol.
Beyond the mentioned component, also can contain reactive diluent, solvent, reach thixotropy imparting agent etc.Specifically can butylphenyl glycidyl ether be arranged illustrative reactive diluent, solvent has methyl ethyl ketone, and the thixotropy imparting agent has organic modified bentonite.
The better fit ratio of anion exchanger of the present invention is 0.1～10 weight portion with respect to per 100 weight portion resin composition for electronic part sealing, is preferable with 1～5 weight portion.During less than 0.1 weight portion, anion removes that the lifting effect of property, moisture-proof reliability etc. is relatively poor, and on the other hand, during greater than 10 weight portions, its effect can more not improve, and can increase cost on the contrary and not good.
By with inorganic cation permutoid and anion exchanger of the present invention and usefulness, can increase the anion capturing ability of anion exchanger of the present invention, and be expected to obtain the seizure effect of cationic ion.The inorganic cation permutoid is the inorganic matter with cation exchange.
The allotment ratio of anion exchanger of the present invention and inorganic cation permutoid is not particularly limited, and weight ratio is good with 100:0～20:80.The allotment of anion exchanger of the present invention and inorganic cation permutoid can be allocated respectively when the preparation resin composition for electronic part sealing, carries out after also can in advance they evenly being mixed.To use mixture is preferable.Because can further bring into play by this and with the effect of these compositions.
As the concrete example of inorganic cation permutoid, can enumerate metaantimmonic acid (antimony pentaoxide hydrate), niobic acid (niobium pentoxide hydrate), Mn oxide, basic zirconium phosphate, titanium phosphate, phosphoric acid tin, cerous phosphate, zeolite and be stained with mineral etc.With metaantimmonic acid (antimony pentaoxide hydrate), basic zirconium phosphate, and titanium phosphate be good.
Resin composition for electronic part sealing of the present invention, can easily obtain by utilizing known method mixing above-mentioned raw materials, for example, suitably allocate above-mentioned each raw material and place muller under heated condition, to mix this composite, make semi-solid preparation shape resin combination, at room temperature, use well-known method to pulverize, carry out briquetting in case of necessity and obtain after its cooling.
Anion exchanger of the present invention can be used in electronic device or the encapsulation of electric component, lining, and various uses such as insulation.
And then, also can use anion exchanger of the present invention in the stabilizing agent of resins such as vinyl chloride, the antirust agent etc.
Allotment has the used for electronic device resin combination of anion exchanger of the present invention, can be used in the member that is mounted with elements such as passive elements such as active components such as semiconductor chip, transistor, diode, IGCT, capacitor, resistive element, coil on supporting members such as lead-frame, the band conveyor (tape carrier) that has connected up, wiring plate, glass, silicon wafer etc.In addition, also can use resin composition for electronic part sealing of the present invention effectively on the printed circuit board (PCB).Allotment has the used for sealing electronic device composition epoxy resin of anion exchanger of the present invention can use too.
As the method for using resin composition for electronic part sealing of the present invention or used for sealing electronic device composition epoxy resin that element is encapsulated, the most common is low pressure transfer molding method, also can use injection moulding, compression forming method etc.
Application on zero wiring plate
Usually, utilize the Thermocurable of epoxy resin etc. to make after the printed circuit board, the Copper Foil of adhering in the above carries out etching and processing to it and waits and make circuit, makes wiring plate thus.But owing to densification, stackedization of circuit and the filming of insulating barrier etc. of circuit, burn into defective insulation etc. becomes problem in recent years.When making wiring plate, can prevent this corrosion by adding anion exchanger of the present invention.In addition, also can prevent corrosion of wiring plate etc. in the insulating barrier that wiring plate is used by adding anion exchanger of the present invention.Because so, the wiring plate that contains anion exchanger of the present invention can suppress the generation by caused defective products such as corrosion.Resin solid composition 100 weight portions in the insulating barrier of using with respect to this wiring plate or wiring plate, it is good to add 0.1～5 weight portion anion exchanger of the present invention.At this, also can contain the inorganic cation permutoid.
Zero allotment in bonding agent
Usually, use bonding agent on substrates such as wiring plate, to assemble electronic device etc.By adding anion exchanger of the present invention in the employed bonding agent at this moment, can suppress to result from the generation of the defective products of corrosion etc.With respect to resin solid composition 100 weight portions in this bonding agent, be good to add 0.1～5 weight portion anion exchanger of the present invention.At this, also can contain the inorganic cation permutoid.
Add anion exchanger of the present invention in the employed conductive adhesive when on wiring plate, connecting electronic device or wiring, can suppress to result from the generation of the defective products of corrosion etc.As this conductive adhesive, can enumerate the bonding agent of conductive metal such as argentiferous.With respect to resin solid composition 100 weight portions in this conductive adhesive, be good to add 0.1～5 weight portion anion exchanger of the present invention.At this, also can contain the inorganic cation permutoid.
Zero allotment in varnish
Can use the varnish that contains anion exchanger of the present invention to make electrical apparatus product, printed wiring board or electronic device etc.Can enumerate with the material of heat-curing resins such as epoxy resin as this varnish as principal component.With respect to these resin solid composition 100 weight portions, be good to add 0.1～5 weight portion anion exchanger of the present invention.At this, also can contain the inorganic cation permutoid.
Zero allotment in creme
Can in containing the cream of silver powder etc., add anion exchanger of the present invention.Creme be that the accessory agent as soldering etc. uses, be used to improve the bonding material between the continuous metal.By this, can suppress the generation of the corrosive substance that generates by creme.With respect to resin solid composition 100 weight portions in this creme, be good to add 0.1～5 weight portion anion exchanger of the present invention.At this, also can contain the inorganic cation permutoid.
＜embodiment 〉
Be described more specifically the present invention with embodiment below.The present invention is not subjected to the restriction of following embodiment certainly, meeting under the situation of aforementioned, scope described later, can suitably change, these changes are included in the technical scope of the present invention, and in addition, the M of 0.1M represents molar concentration, % represents weight %, part expression weight portion.
＜synthesis example 1 〉
Will be by composition formula Mg
4.5Al
2(OH)
13CO
33.5H
2The hydrotalcite compound (being called MAH1) that O is represented 550 ℃ of calcinings 2 hours, obtains by Mg
0.7Al
0.3O
1.15Form represented hydrotalcite calcined material (being called tMAH1).
Zero calcining test
Measure the mass change (thermal mass assay determination TG-DTA, measure in 20 ℃/minute of 30～530 ℃ of the temperature ranges, programming rate, in atmosphere, measure) of the caused MAH1 of heating.This result as shown in Figure 1.
Can know at temperature calcined hydrotalcite compound by Fig. 1, can't obtain calcining effect than 240 ℃ lower.
＜synthesis example 2 〉
Will be by composition formula Ni
4.5Al
2(OH)
13CO
33.5H
2The hydrotalcite compound (being called NAH) that O is represented 550 ℃ of calcinings 2 hours, obtains by Ni
0.7Al
0.3O
1.15The represented hydrotalcite calcined material (being called tNAH) of composition.
＜synthesis example 3 〉
Will be by composition formula Zn
4.5Al
2(OH)
13CO
33.5H
2The hydrotalcite compound (being called ZAH) that O is represented 550 ℃ of calcinings 2 hours, obtains by Zn
0.7Al
0.3O
1.15The represented hydrotalcite calcined material (being called tZAH) of composition.
＜embodiment 1 〉
In the 0.1M of the 2000ml sodium metasilicate aqueous solution, add the tMAH1 of 100 grams, after 4 hours, filter, wash 90 ℃ of stirrings.After being dried, obtained anion exchanger (anion exchanger 1) in 2 hours 550 ℃ of calcinings.
＜embodiment 2 〉
In the 10% 4 different third titanium oxide aqueous isopropanol of 160 grams, add the tMAH1 of 100 grams.In this solution, add water 10ml, stir a whole night, filter, wash.Through 3 days air-dry after, obtained anion exchanger (anion exchanger 2) in 2 hours 550 ℃ of calcinings.
＜embodiment 3 〉
In tetramethoxy-silicane 10% methanol solution 160 gram, add the tMAH1 of 100 grams, stir a whole night, through 1 day air-dry after, obtained anion exchanger (anion exchanger 3) in 2 hours 550 ℃ of calcinings.
＜embodiment 4 〉
The limit uses agitator to stir the tMAH1 of 100 grams, and the tetramethoxy-silicane of 16 grams is added on the limit.Stir once more, through 1 day air-dry after, obtained anion exchanger (anion exchanger 4) in 2 hours 550 ℃ of calcinings.
＜embodiment 5 〉
In 0.1M zirconium oxychloride aqueous solution 2000ml, add the tNAH of 100 grams, use the 0.1M ammonia spirit to be adjusted into pH8, stir this solution a whole night, filter, washing.After being dried, obtained anion exchanger (anion exchanger 5) in 2 hours 550 ℃ of calcinings.
＜embodiment 6 〉
In tetraethoxysilane 10% ethanolic solution 160 gram, add the tZAH of 100 grams, stir a whole night, through 1 day air-dry after, obtained anion exchanger (anion exchanger 6) in 2 hours 550 ℃ of calcinings.
＜embodiment 7 〉
In 0.1M sodium metasilicate aqueous solution 2000ml, add the MAH1 of 100 grams, after 4 hours, filter, wash 90 ℃ of stirrings.After being dried, obtained anion exchanger (anion exchanger 7) in 2 hours 550 ℃ of calcinings.
＜embodiment 8 〉
In the 10% different third titanium oxide aqueous isopropanol, 160 grams, add the MAH1 of 100 grams.In this solution, add water 10ml, stir a whole night, filter, wash.Through 3 days air-dry after, obtained anion exchanger (anion exchanger 8) in 2 hours 550 ℃ of calcinings.
＜embodiment 9 〉
The ZAH of 100 grams are stirred with agitator in the limit, and the tetramethoxy-silicanes of 16 grams are added on the limit, stir once more, through 1 day air-dry after, obtained anion exchanger (anion exchanger 9) in 2 hours 550 ℃ of calcinings.
The mensuration of zero hygroscopicity and chloride ion exchangeability
The anion exchanger of following table 1, is placed it in the atmosphere after 4 hours 150 ℃ of heating, and gravimetry is investigated hygroscopicity over time.
In the 0.1M of 50ml hydrochloric acid, add the anion exchanger of the following table 1 of 1 gram respectively, stirred 24 hours at 40 ℃.Subsequently, filter, use ion chromatography analysis to measure chloride ion concentration in the filtrate, draw the chloride ion exchange capacity of per 1 gram sample.Its result is as shown in table 1.
[table 1]
Though can know that by table 1 anion exchange capacity of anion exchanger of the present invention is lower than hydrotalcite calcined material, but hygroscopicity is low, and the anion exchange performance is good than hydrotalcite compound, for being fit to be used in the good anion exchanger of used for sealing electronic device composition epoxy resin etc.
＜embodiment 10 〉
In 80 parts of cresols-novolac type epoxy resin (epoxide equivalent 235), 20 parts of bromination phenol-novolac type epoxy resin (epoxide equivalent 275), 50 parts of phenol-novolac resins (molecular weight 700～1000), 2 parts of triphenylphosphines, 1 part of Brazil wax, 1 part of carbon black and 370 parts of fused silica, allocate 5 parts of anion exchangers 2, cooling after its hot-rolling with 80 ℃～90 ℃ mixed 3～5 minutes, pulverize, obtain the powder epoxy resin composition.It is handled with 100 purposes sieve, use the sample that passes through, the molding condition is 170 ℃, 3 minutes, encapsulates the moisture-proof reliability evaluation element that is connected with the aluminium wiring.
To this element that has encapsulated, implement pressure cooker testing at 125 ℃, measure the time that broken string takes place.In addition, 50 samples of the middle use of this test are asked its mean value.In addition, use the IR reflow ovens of 245 ℃ of maximum temperatures to come this element that has encapsulated of heat treated, observe its outward appearance.Its result has been shown in the table 2.
＜embodiment 11 〉
Use anion exchanger 3 to come the anion exchanger 2 of alternate embodiment 10, all the other carry out same operation and make the evaluation sample.Then, carry out same evaluation, its result such as table 2.
＜embodiment 12 〉
Use anion exchanger 4 to come the anion exchanger 2 of alternate embodiment 10, all the other carry out same operation and make the evaluation sample.Then, carry out same evaluation, its result such as table 2.
＜embodiment 13 〉
Use anion exchanger 5 to come the anion exchanger 2 of alternate embodiment 10, all the other carry out same operation and make the evaluation sample.Then, carry out same evaluation, its result such as table 2.
＜embodiment 14 〉
Use anion exchanger 6 to come the anion exchanger 2 of alternate embodiment 10, all the other carry out same operation and make the evaluation sample.Then, carry out same evaluation, its result such as table 2.
＜embodiment 15 〉
The metaantimmonic acid (weight ratio is 5:5) that uses anion exchanger 4 and belong to the inorganic cation permutoid comes the anion exchanger 2 of alternate embodiment 10, and all the other carry out same operation and make the evaluation sample.Then, carry out same evaluation, its result such as table 2.
＜embodiment 16 〉
The basic zirconium phosphate (weight ratio is 7:3) that uses anion exchanger 5 and belong to the inorganic cation permutoid comes the anion exchanger 2 of alternate embodiment 10, and all the other carry out same operation and make the evaluation sample.Then, carry out same evaluation, its result such as table 2.
＜comparative example 1 〉
Use MAH1 to come the anion exchanger 2 of alternate embodiment 10, all the other carry out same operation and make the evaluation sample.Then, carry out same evaluation, its result such as table 2.
＜comparative example 2 〉
Use tMAH1 to come the anion exchanger 2 of alternate embodiment 10, all the other carry out same operation and make the evaluation sample.Then, carry out same evaluation, its result such as table 2.
＜comparative example 3 〉
Except not using anion exchanger 2, all the other and embodiment 10 carry out same operation and make the evaluation sample.Then, carry out same evaluation, its result such as table 2.
[table 2]
| No. | Sample | The broken string time (hour) | Outward appearance after the heat treated |
| Embodiment 10 | Anion exchanger 2 | 500 | No change |
| Embodiment 11 | Anion exchanger 3 | 520 | No change |
| Embodiment 12 | Anion exchanger 4 | 600 | No change |
| Embodiment 13 | Anion exchanger 5 | 500 | No change |
| Embodiment 14 | Anion exchanger 6 | 530 | No change |
| Embodiment 15 | Anion exchanger 4+ |
600 | No change |
| Embodiment 16 | Anion exchanger 5+ |
600 | No change |
| Comparative example 1 | MAH1 | 250 | No change |
| Comparative example 2 | tMAH1 | 430 | Be full of cracks is arranged |
| Comparative example 3 | Do not have | 150 | No change |
＜embodiment 17 〉
Mix 60 parts of bisphenol A type epoxy resins (rising sun vapour crust (strain) system, trade name: ARARUDAITAER-2502) as epoxy resin, 30 parts of butylphenyl glycidyl ether are as reactive diluent, 20 parts of epoxy amine addition reactions (epoxy amine additive compound) (Asahi Chemical Industry's industry (strain) system, trade name: NOBAKYUA HX-3721) as curing agent, 1 part of organic modified bentonite is as the thixotropy imparting agent, 30 parts of talcums are as inorganic filler, 8 parts of synthetic zeolites, 0.5 part red pigment, and 3 parts of anion exchangers 9, use three roller mixers that solids are scattered in the resin equably, obtain the surface-assembled adhesive composite.Assessment so the composition that forms of modulation insulating reliability, lead a property, projects such as coating shape, cementability and gelling time, result such as table 3.
＜comparative example 4 〉
The surface-assembled of embodiment 17 with adhesive composite in except not adding anion exchanger 9, all the other and embodiment 17 carry out same operation and make.Then, carry out same assessment, its result such as table 3.
Zero insulating reliability
Measure surface-assembled that embodiment 17 and comparative example 4 modulated surface insulation resistance value according to JIS-Z-3197 with the solidfied material of adhesive composite.
Also promptly, on II type comb shape substrate, using the silk screen print method coating film thickness is the described composition of 100～150 μ m, makes its curing in 10 minutes 150 ℃ of heating.Use the Weak current analyzer to measure the insulating resistance value (A value) of gained untreatment base.Then, in water, this substrate boiled 2 hours after, under 25 ℃, the environment of 60%RH, placed about 1 hour, measure insulating resistance value (B value) once more.This evaluation criterion is:
A/B ≦ 10
2For " zero ",
10
2＜A/B ≦ 10
3For " △ ",
10
3＜A/B is " * ".
Its result such as table 3.
Zero leads a property
Use distributor, on the glass epoxy substrate that prints comprehensively and be solidified with solder resist (FR-4), with per 1: 0.15 milligram, coating speed is the condition of per 1 50msec, adhesive composite to embodiment 17 and comparative example 4 manufacturings carries out continuous coated test at 1000, even 1 position only takes place also be evaluated as " * " because of leading a caused substrate contamination of property, 1 position is evaluated as " zero " when all not taking place.
Zero coating shape
At the above-mentioned taper shape that is shaped as that leads the adhesive composite that is coated with in the evaluation of property, use microscopic examination also to measure the bottom surface diameter D of this circular cone and the height H of circular cone, the ratio H/D of height and diameter exists
0.5 following is " * ",
0.5～1.5 scopes be " zero ",
1.5 that above is " △ ".
Zero cementability
To lead a property the same with evaluation, printing comprehensively and be solidified with bonding 2125 resistance chips on the glass epoxy substrate of solder resist, by push away-the La meter measures 1 chip drawn back needed strength.Also promptly, used following element, that is, the adhesive composite of 0.3 milligram of embodiment 17 of coating and comparative example 4 manufacturings on per 1 chip, heating made the element of its curing in 3 minutes in 150 ℃ baking oven.
Zero gluing time
Use 150 ℃ hot plate to heat the embodiment 17 of 0.3 ± 0.05 gram and the bonding agent of comparative example 4 manufacturings, measure the flow regime disappearance and reach the needed time of gelatine (second).
[table 3]
| Composition epoxy resin | Embodiment 17 | Comparative example 4 |
| Bisphenol A type epoxy resin | 60.0 | 60.0 |
| Reactive diluent | 30.0 | 30.0 |
| The epoxy amine addition product | 20.0 | 20.0 |
| Organic modified bentonite | 1.0 | 1.0 |
| Talcum | 30.0 | 30.0 |
| Synthetic zeolite | 8.0 | 8.0 |
| Red pigment | 0.5 | 0.5 |
| Anion exchanger 9 | 3.0 | - |
| Insulating reliability | ○ | × |
| Lead a property | ○ | ○ |
| The coating shape | ○ | ○ |
| Cementability (kg) | 4.5 | 4.1 |
| Gelling time (second) | 60 | 60 |
＜embodiment 18 〉
Use following composition and operation to modulate the sealing liquid crystal material.With 100 parts of bisphenol A type epoxy resins (rising sun vapour crust (strain) system, trade name: ARARUDAIT AER-2502) as epoxy resin, 40 parts of epoxy amine additive compound (Asahi Chemical Industry's industry (strain) systems, trade name: NOBAKYUA HX-3721) as curing agent, 60 parts of titanium oxide (the former industry of stone (strain) systems, trade name: DAIBEK R-630) as filler, 5 parts of cataloid (Japanese A Yeluojilu industry (strain) systems, trade name: AEROSILR-974), 1 part of metaantimmonic acid is as the inorganic cation permutoid, and 2 parts of anion exchangers 6, with dalton's agitator 40 ℃ of heating, stir and mixed in 30 minutes.Subsequently, use three roller mixers to grind 5 times, the particle diameter that use grinding pin is confirmed content adds the silica separaant of 1.5 parts of particle diameters, 5 μ m and makes its even dispersion below 5 μ m, obtains the composition as the sealing liquid crystal material.
By serigraphy, will enclose the sealing that the form of mouth is printed on the glass substrate that is formed with ITO (transparency electrode) to remain with liquid crystal at this resulting sealing liquid crystal material.Then 80 ℃ of heating, kept 3 minutes, after preparing dry and the fusion of substrate being adhered, be returned to room temperature.Then combine, use the hot press crimping 10 minutes that is heated to 130 ℃, the sealing material is solidified with glass substrate to utmost point side.Will be after this resulting blank panel vacuumize, liquid crystal (Mei Luke society system, ZL11636) is injected, use the sealing material to enclose and mouthful seal, make its curing and obtain liquid crystal panel.
Estimate the liquid crystal aligning of this liquid crystal panel and storage property (with respect to the intensity that just applies after the pulse voltage, can keep seeing through the ratio of luminous intensity for a long time, can descend when having impurity to exist).When estimating the liquid crystal electrical orientation, under the condition that does not apply voltage, this liquid crystal board is heated to 80 ℃, sees through the width that occurs near the black-tape the sealing material when Polarizer is observed and estimate by observing.Width is that 0.5mm is " △ ", is " * " greater than 1mm for " zero ", 0.5～1mm when following.The result is as shown in table 4.
＜comparative example 5 〉
Do not add metaantimmonic acid and anion exchanger 6 in the composition of embodiment 18, all the other similarly make liquid sealing material composition.And and embodiment 18 similarly estimates.Result such as table 4.
[table 4]
| Composition epoxy resin | Embodiment 18 | Comparative example 5 |
| Bisphenol A type epoxy resin | 100 | 100 |
| The epoxy amine addition product | 40 | 40 |
| Titanium oxide | 60 | 60 |
| Cataloid | 5 | 5 |
| Metaantimmonic acid | 1 | - |
| Anion exchanger 6 | 2 | - |
| Liquid crystal aligning | ○ | × |
| Storage property (%) | 95 | 42 |
＜embodiment 19 〉
To 100 parts of epoxide equivalents is 450～500 bisphenol A type epoxy resin (rising sun vapour crust (strain) system, trade name: ARARUDAITAER-2502) add 5 parts of anion exchangers 9, add again 4 parts of dicyandiamides as epoxy hardener, 0.4 part of benzyl dimethylamine as curing accelerator, 60 parts of solvents (methyl ethyl ketone), mix and manufacture the impregnation resin varnish.Then make the electric resin varnish of making just now with the glass cloth impregnation of low alkali of thickness 0.2mm.Subsequently, made preliminary-dip piece in 5 minutes 160 ℃ of dryings.The size, 6 that this preliminary-dip piece are cut into 50mm * 50mm overlap, and are 30kg/cm with the initial stage condition
2, 160 ℃, 15 minutes, be 70kg/cm subsequently
2, heating in 165 ℃, 1 hour, pressurization condition, the volume fraction that obtains resin and glass cloth base material is the plywood that 50:50, thickness are about 1.6mm.
Use silk screen print method on plywood, to be coated with silver paste (the system DODAITXA208 of Fujikura Kasei Co., Ltd),, form 2 printed wiring conductors (electrode) that are comb shape in opposite directions by being heating and curing 1 hour at 130 ℃.This interelectrode beeline all is 1mm, and thickness is about 20 μ m.In order to estimate the effect that prevents that ELECTROMIGRATION PHENOMENON from taking place, to applying the DC voltage of 100V between this 2 comb poles, remain on 40 ℃, 95%RH simultaneously, measuring interelectrode insulating resistance value becomes 10
6Time below the Ω is as the time that forms short circuit.
As a result, forming short circuit duration is more than 3000 hours.
＜comparative example 6 〉
Do not add anion exchanger 9 in the resin varnish of embodiment 19, all the other carry out same operation and make resin varnish, and make plywood.This plywood is carried out evaluation result similarly to Example 19, and forming short circuit duration is 160 hours.
＜embodiment 20 〉
With the part by weight of 1:2 mixed t MAH1 and magnesia (rock paddy chemical industry system, MTK-30, following magnesia use identical material) fully, as anion exchange composition 1-0.
＜embodiment 21 〉
With the part by weight of 1:1 mixed t MAH1 and magnesia fully, as anion exchange composition 1-1.
＜embodiment 22 〉
With the part by weight of 3:2 mixed t MAH1 and magnesia fully, as anion exchange composition 1-2.
＜embodiment 23 〉
With the part by weight of 2:1 mixed t MAH1 and magnesia fully, as anion exchange composition 1-3.
＜embodiment 24 〉
With 700 ℃, 2 hours calcining MAH1, as anion exchanger A-1, when measuring the composition of this anion exchanger A-1, it was for consisting of Mg0
7Al
0.3O
1.15Material.
＜embodiment 25 〉
In embodiment 24,, carry out identical operations and obtain anion exchanger A-2 except making calcining heat is 800 ℃.Measure the X-ray diffraction of this anion exchanger A-2, the result as shown in Figure 2.In addition, also measure the X-ray diffraction of tMAH1 and MAH1, the result is shown in Fig. 4,5.
＜embodiment 26 〉
In embodiment 24,, carry out identical operations and obtain anion exchanger A-3 except making calcining heat is 900 ℃.
＜embodiment 27 〉
In embodiment 24,, carry out identical operations and obtain anion exchanger A-4 except making calcining heat is 1000 ℃.Measure the X-ray diffraction of this anion exchanger A-4, the result as shown in Figure 3.
In Fig. 2～4, the sharp cutting edge of a knife or a sword of the angle of diffraction 42.9 degree is represented MgO.The sharp cutting edge of a knife or a sword of divalent metal oxide (MgO) can't be confirmed among Fig. 5 (MAH1), more divalent metal oxide can be confirmed to have generated during still with A-2 (Fig. 2) and A-4 (Fig. 3) and tMAH1 (Fig. 4) comparison.In addition, the A-4 in that 1000 ℃ of calcining MAH1 form sharp cutting edge of a knife or a sword occurs at the angle of diffraction 19.0 degree, 31.3 degree, 36.85 degree, 44.8 degree.These can think MgAl
2O
4Sharp cutting edge of a knife or a sword.This MgAl
2O
4The reason that descends for the anion exchange performance of calcined material.
＜embodiment 28 〉
Ratio with 550 ℃, 2 hours calcined magnesium ions and aluminium ion is the hydrotalcite compound of 2.5:1, and as anion exchanger B-1, when measuring the composition of this anion exchanger B-1, it consists of Mg
2.5AlO
4
＜embodiment 29 〉
Ratio with 550 ℃, 2 hours calcined magnesium ions and aluminium ion is the hydrotalcite compound of 2.75:1, and as anion exchanger B-2, when measuring the composition of this anion exchanger B-2, it consists of Mg
2.75AlO
4.25
＜embodiment 30 〉
With 550 ℃, 2 hours calcining Mg
6Al
2(OH)
16CO
34H
2The hydrotalcite compound that O is represented, as anion exchanger B-3, when measuring the composition of this anion exchanger B-3, it consists of Mg
3AlO
4.5
＜embodiment 31 〉
Ratio with 550 ℃, 2 hours calcined magnesium ions and aluminium ion is the hydrotalcite compound of 4:1, and as anion exchanger B-4, when measuring the composition of this anion exchanger B-4, it consists of Mg
4AlO
5.5
＜embodiment 32 〉
Ratio with 550 ℃, 2 hours calcined magnesium ions and aluminium ion is the hydrotalcite compound of 5:1, and as anion exchanger B-5, when measuring the composition of this anion exchanger B-5, it consists of Mg
5AlO
6.5
＜embodiment 33 〉
Ratio with 800 ℃, 2 hours calcined magnesium ions and aluminium ion is the hydrotalcite compound of 3:1, and as anion exchanger B-6, when measuring the composition of this anion exchanger B-6, it consists of Mg
3AlO
4.5
＜embodiment 34 〉
Ratio with 800 ℃, 2 hours calcined magnesium ions and aluminium ion is the hydrotalcite compound of 4:1, and as anion exchanger B-7, when measuring the composition of this anion exchanger B-7, it consists of Mg
4AlO
5.5
＜embodiment 35 〉
Ratio with 800 ℃, 2 hours calcined magnesium ions and aluminium ion is the hydrotalcite compound of 5:1, and as anion exchanger B-8, when measuring the composition of this anion exchanger B-8, it consists of Mg
5AlO
6.5
＜embodiment 36 〉
Zero ion exchange ratio determination test
With the anion exchanger of the following table 5 of 1.0 grams and the polyethylene bottle that the anion exchange composition is put into 100ml, add sodium-chloride water solution and close the fastening of the 0.02M of 50ml again, respectively 40 ℃ of vibrations 24 hours.Subsequently, using hole size is the molecular filter filtering solution of 0.1 μ m, uses ion chromatography analysis to measure the chlorine ion concentration of filtrate.The material of operating and measure chlorine ion concentration with not adding any sample equally compares, and tries to achieve ion exchange ratio.These results are as shown in table 5.In addition, used the pH value of filtrate of anion exchange composition and anion exchanger to be alkalescence.
[table 5]
| No. | Sample | Ion |
| Embodiment | ||
| 20 | Anion exchange composition 1-0 | 90％ |
| Embodiment 21 | Anion exchange composition 1-1 | 98％ |
| Embodiment 22 | Anion exchange composition 1-2 | 99％ |
| Embodiment 23 | Anion exchange composition 1-3 | 98％ |
| Embodiment 24 | Anion exchanger A-1 | 80％ |
| Embodiment 25 | Anion exchanger A-2 | 98％ |
| Embodiment 26 | Anion exchanger A-3 | 95％ |
| Embodiment 27 | Anion exchanger A-4 | 71 |
| Embodiment | ||
| 28 | Anion exchanger B-1 | 71％ |
| Embodiment 29 | Anion exchanger B-2 | 75％ |
| Embodiment 30 | Anion exchanger B-3 | 98％ |
| Embodiment 31 | Anion exchanger B-4 | 99％ |
| Embodiment 32 | Anion exchanger B-5 | 98％ |
| Embodiment 33 | Anion exchanger B-6 | 98％ |
| Embodiment 34 | Anion exchanger B-7 | 95％ |
| Embodiment 35 | Anion exchanger B-8 | 77％ |
| Comparative example | MAH1 | 0％ |
| Comparative example | tMAH1 | 70％ |
| Comparative example | Mg 6Al 2(OH) 16CO 3·4H 2O | 0％ |
| Comparative example | Magnesia | 0％ |
＜embodiment 37 〉
As employed resin of following allotment used for electronic device encapsulation material etc. and anion exchange composition 1-2, use 80 ℃～90 ℃ hot-rollings that it was mixed 3～5 minutes.
80 parts in cresols-novolac type epoxy resin (epoxide equivalent 235)
20 parts of bromination phenol-novolac type epoxy resin (epoxide equivalent 275)
50 parts of phenol-novolac resins (molecular weight 700～1000)
2 parts of triphenylphosphines
1 part of Brazil wax
1 part of carbon black
370 parts of fused silica
2 parts of anion exchange composition 1-2
Subsequently, cooling, pulverizing obtain powder epoxy resin composition A-1-2.Subsequently, A-1-2 sieves with 100 mesh sieves with this composition, makes and has passed through 100 purpose samples.
Use this to pass through 100 purpose samples, at 170 ℃ it is solidified and make the resin body A-1-2 that mixes.This resin body A-1-2 that mixes is ground into 2～3mm size.Use this pulverizing sample to carry out the chlorion dissolution test.
＜embodiment 38 〉
Except the anion exchange composition 1-2 that uses anion exchanger A-2 alternate embodiment 37 and embodiment 37 carry out same operation, make the resin body A-2-2 that mixes.Subsequently and embodiment 37 similarly pulverize and make the pulverizing sample.
＜embodiment 39 〉
Except the anion exchange composition 1-2 that uses anion exchanger B-3 alternate embodiment 37 and embodiment 37 carry out same operation, make the resin body A-3-3 that mixes.Subsequently and embodiment 37 similarly pulverize and make the pulverizing sample.
＜comparative example 7 〉
Except the anion exchange composition 1-2 that uses MAH1 alternate embodiment 37 and embodiment 37 carry out same operation, make the comparison resin body A-1 that mixes.Subsequently and embodiment 37 similarly pulverize and make the pulverizing sample.
＜comparative example 8 〉
Except the anion exchange composition 1-2 that uses tMAH1 alternate embodiment 37 and embodiment 37 carry out same operation, make the comparison resin body A-2 that mixes.Subsequently and embodiment 37 similarly pulverize and make the pulverizing sample.
＜comparative example 9 〉
Except using composition formula to be Mg
6Al
2(OH)
16CO
34H
2Beyond the anion exchange composition 1-2 of the hydrotalcite compound alternate embodiment 37 of O and embodiment 37 carry out same operation, make the comparison resin body A-3 that mixes.Subsequently and embodiment 37 similarly pulverize and make the pulverizing sample.
＜comparative example 10 〉
Except not using anion exchange composition 1-2 and embodiment 37 carry out same operation, make the comparison resin body A that mixes.Subsequently and embodiment 37 similarly pulverize and make the pulverizing sample.Also promptly, relatively resin mixes and does not contain calcined composition among the body A.
＜embodiment 40 〉
As employed resin of following allotment used for electronic device encapsulation material etc. and anion exchange composition 1-2, use 80 ℃～90 ℃ hot-rollings that it was mixed 3～5 minutes.
80 parts in cresols-novolac type epoxy resin (epoxide equivalent 235)
20 parts of bromination phenol-novolac type epoxy resin (epoxide equivalent 275)
50 parts of phenol-novolac resins (molecular weight 700～1000)
3 parts of DBU
Amine is 3 parts of silane coupling agents (3-TSL 8330)
1 part of Brazil wax
1 part of carbon black
370 parts of fused silica
2 parts of anion exchanger 1-2
Subsequently, cooling, pulverizing obtain powder epoxy resin composition B-1-2.Subsequently, B-1-2 sieves with 100 mesh sieves with this composition, makes and has passed through 100 purpose samples.
Use this to pass through 100 purpose samples, at 170 ℃ it is solidified and make the resin body B-1-2 that mixes.This resin body B-1-2 that mixes is ground into 2～3mm size.Use this pulverizing sample to carry out the chlorion dissolution test.
＜embodiment 41 〉
Except the anion exchange composition 1-2 that uses anion exchanger A-2 alternate embodiment 40 and embodiment 40 carry out same operation, make the resin body B-2-2 that mixes.Subsequently and embodiment 40 similarly pulverize and make the pulverizing sample.
＜embodiment 42 〉
Except the anion exchange composition 1-2 that uses anion exchanger B-3 alternate embodiment 40 and embodiment 40 carry out same operation, make the resin body B-3-3 that mixes.Subsequently and embodiment 40 similarly pulverize and make the pulverizing sample.
＜comparative example 11 〉
Except the anion exchange composition 1-2 that uses MAH1 alternate embodiment 40 and embodiment 40 carry out same operation, make the comparison resin body B-1 that mixes.Subsequently and embodiment 40 similarly pulverize and make the pulverizing sample.
＜comparative example 12 〉
Except the anion exchange composition 1-2 that uses tMAH1 alternate embodiment 40 and embodiment 40 carry out same operation, make the comparison resin body B-2 that mixes.Subsequently and embodiment 40 similarly pulverize and make the pulverizing sample.
＜comparative example 13 〉
Except using composition formula to be Mg
6Al
2(OH)
16CO
34H
2Beyond the anion exchange composition 1-2 of the hydrotalcite compound alternate embodiment 40 of O and embodiment 40 carry out same operation, make the comparison resin body B-3 that mixes.Subsequently and embodiment 40 similarly pulverize and make the pulverizing sample.
＜comparative example 14 〉
Except not using anion exchange composition 1-2 and embodiment 40 carry out same operation, make the comparison resin body B that mixes.Subsequently and embodiment 40 similarly pulverize and make the pulverizing sample.Also promptly, relatively resin mixes body B for not containing the material of calcined composition.
＜embodiment 43 〉
Zero from the mix test of body extraction chlorion of resin
Each resin that adds above-mentioned manufacturing in polytetrafluoroethylene (PTFE) system pressure vessel mix body or comparison resin mix body 5 grams and pure water 50ml and airtight were 125 ℃ of heating 100 hours.After the cooling water is taken out, use ion chromatography analysis to be determined at the chlorine ion concentration of stripping in the water.These results are as shown in table 6.
[table 6]
| No. | Sample | Chlorine ion concentration (ppm) | PH |
| Embodiment 37 | The resin body A-1-2 that mixes | 19 | 4.6 |
| Embodiment 38 | The resin body A-2-2 that mixes | 19 | 4.6 |
| Embodiment 39 | The resin body A-3-3 that mixes | 20 | 4.6 |
| Comparative example 7 | The resin body A-1 that mixes relatively | 56 | 4.3 |
| Comparative example 8 | The resin body A-2 that mixes relatively | 25 | 4.5 |
| Comparative example 9 | The resin body A-3 that mixes relatively | 55 | 4.3 |
| Comparative example 10 | The resin body A that mixes relatively | 60 | 4.2 |
| Embodiment 40 | The resin body B-1-2 that mixes | 20 | 6.8 |
| Embodiment 41 | The resin body B-2-2 that mixes | 22 | 6.8 |
| Embodiment 42 | The resin body B-3-3 that mixes | 22 | 6.8 |
| Comparative example 11 | The resin body B-1 that mixes relatively | 61 | 6.7 |
| Comparative example 12 | The resin body B-2 that mixes relatively | 55 | 6.8 |
| Comparative example 13 | The resin body B-3 that mixes relatively | 60 | 6.7 |
| Comparative example 14 | The resin body B that mixes relatively | 62 | 6.8 |
Can know from table 5 and table 6, near the ion exchange ratio height of anion exchanger of the present invention neutrality, even make an addition to encapsulation timber fat, even the pH value slant acidity or the partial neutral of encapsulation material composition extract all have the effect of the stripping that suppresses chlorion.By this, can in relative broad range, provide reliability high encapsulation material composition.
＜embodiment 44 〉
In 10% methanol solution, 200 grams of methyl silicate (methyl silicate) monomer (rub chemistry system) more, add 100 gram tMAH1, stirred for 1 night after, air-dry 1 day.Subsequently, it was calcined 2 hours, obtain anion exchanger (anion exchanger 10) with 550 ℃.
＜embodiment 45 〉
In 10% methanol solution, 160 grams of methyl silicate oligomer (the chemistry system of rubbing, trade name METHYLSILICATE 51 below use phase jljl more), add 100 gram tMAH1, stirred for 1 night after, air-dry 1 day.Subsequently, it was calcined 2 hours, obtain anion exchanger (anion exchanger 11) with 550 ℃.
＜embodiment 46 〉
In 10% methanol solution, 200 grams of methyl silicate monomer (rub chemistry system) more, add 100 gram anion exchanger B-3, stirred for 1 night after, air-dry 1 day.Subsequently, it was calcined 2 hours, obtain anion exchanger (anion exchanger B-9) with 550 ℃.
＜embodiment 47 〉
In 10% methanol solution, 160 grams of methyl silicate oligomer (rub chemistry system) more, add 100 gram anion exchanger B-3, stirred for 1 night after, air-dry 1 day.Subsequently, it was calcined 2 hours, obtain anion exchanger (anion exchanger B-10) with 550 ℃.
＜embodiment 48 〉
By mixing the magnesia that 60 gram anion exchangers 10 and 40 grams belong to the divalent metal oxide, obtain anion exchanger (anion exchange composition 1-5).
＜embodiment 49 〉
By mixing the magnesia that 60 gram anion exchangers 11 and 40 grams belong to the divalent metal oxide, obtain anion exchanger (anion exchange composition 1-6).
＜embodiment 50 〉
By mixing the magnesia that 60 gram tMAH1 and 40 grams belong to the divalent metal oxide, obtain anion exchanger (anion exchange composition 1-4).
＜embodiment 51 〉
In 10% methanol solution, 200 grams of methyl silicate oligomer (rub chemistry system) more, add 100 gram anion exchange composition 1-4, stirred for 1 night after, air-dry 1 day.Subsequently, it was calcined 2 hours, obtain anion exchanger (anion exchange composition 1-7) with 550 ℃.
＜embodiment 52 〉
In 10% methanol solution, 160 grams of methyl silicate oligomer (rub chemistry system) more, add 100 gram anion exchange composition 1-4, stirred for 1 night after, air-dry 1 day.Subsequently, it was calcined 2 hours, obtain anion exchanger (anion exchange composition 1-8) with 550 ℃.
＜embodiment 53 〉
By mixing the magnesia that 60 gram anion exchanger B-3 and 40 grams belong to the divalent metal oxide, obtain anion exchanger (anion exchange composition 2-1).
＜embodiment 54 〉
By mixing the magnesia that 60 gram anion exchanger B-9 and 40 grams belong to the divalent metal oxide, obtain anion exchanger (anion exchange composition 2-2).
＜embodiment 55 〉
By mixing the magnesia that 60 gram anion exchanger B-10 and 40 grams belong to the divalent metal oxide, obtain anion exchanger (anion exchange composition 2-3).
＜embodiment 56 〉
In 10% methanol solution, 200 grams of methyl silicate monomer (rub chemistry system) more, add 100 gram anion exchange composition 2-1, stirred for 1 night after, air-dry 1 day.Subsequently, it was calcined 2 hours, obtain anion exchanger (anion exchange composition 2-4) with 550 ℃.
＜embodiment 57 〉
In 10% methanol solution, 160 grams of methyl silicate oligomer (rub chemistry system, METH ' YLSILICATE 51) more, add 100 gram anion exchange composition 2-1, stirred for 1 night after, air-dry 1 day.Subsequently, it was calcined 2 hours, obtain anion exchanger (anion exchange composition 2-5) with 550 ℃.
＜embodiment 58 〉
Zero wettability test
Respectively 150 ℃ to heating such as the anion exchanger of remembering table 7 down and anion exchange compositions after 4 hours, these are placed in humidity 90%, 35 ℃ the environment, measure through the weight behind the different time and investigate hygroscopicity (weight increase).The result of their weight increases after 24 hours is as shown in table 7.
Zero ion exchange ratio determination test
With the anion exchanger of the following table 7 of 1.0 grams and the polyethylene system bottle that the anion exchange composition is put into 100ml, add sodium-chloride water solution and close the fastening of the 0.02M of 50ml again, respectively 40 ℃ of vibrations 24 hours.Subsequently, using hole size is the molecular filter filtering solution of 0.1 μ m, uses the chlorine ion concentration in the ion chromatography analysis mensuration filtrate.For the substance-measuring chlorine ion concentration that does not add anion exchanger etc. and operate equally.Compare with it, try to achieve the ion exchange ratio of anion exchanger etc.Its result is as shown in table 7.
[table 7]
| No. | Sample | Weight increase | Ion exchange ratio |
| Embodiment 44 | Anion exchanger 10 | 8％ | 70％ |
| Embodiment 45 | Anion exchanger 11 | 4％ | 67％ |
| Embodiment 30 | Anion exchanger B-3 | 47％ | 97％ |
| Embodiment 46 | Anion exchanger B-9 | 11％ | 71％ |
| Embodiment 47 | Anion exchanger B-10 | 7％ | 70％ |
| Embodiment 50 | Anion exchange composition 1-4 | 43％ | 98％ |
| Embodiment 48 | Anion exchange composition 1-5 | 12％ | 95％ |
| Embodiment 49 | Anion exchange composition 1-6 | 6％ | 95％ |
| Embodiment 51 | Anion exchange composition 1-7 | 11％ | 71％ |
| Embodiment 52 | Anion exchange composition 1-8 | 5％ | 66％ |
| Embodiment 53 | Anion exchange composition 2-1 | 45％ | 99％ |
| Embodiment 54 | Anion exchange composition 2-2 | 12％ | 96％ |
| Embodiment 55 | Anion exchange composition 2-3 | 8％ | 96％ |
| Embodiment 56 | Anion exchange composition 2-4 | 10％ | 67％ |
| Embodiment 57 | Anion exchange composition 2-5 | 6％ | 65％ |
| Comparative example | tMAH1 | 45％ | 70％ |
| Comparative example | MAH1 | 1％ | 0％ |
＜embodiment 59 〉
Following allotment is used in the composition and the anion exchange composition 1-5 of used for electronic device encapsulation material, uses mix this composite 3～5 minutes of 80 ℃～90 ℃ hot-rolling.
80 parts in cresols-novolac type epoxy resin (epoxy resin equivalent 235)
20 parts of bromination phenol-novolac type epoxy resin (epoxy resin equivalent 275)
50 parts of phenol-novolac resins (molecular weight 700～1000)
2 parts of triphenylphosphines
1 part of Brazil wax
1 part of carbon black
370 parts of fused silica
2 parts of anion exchange composition 1-5
Subsequently, cooling, pulverizing obtain powder epoxy resin composition A-Z-1.Then, use 100 purposes sieve that said composition A-Z-1 is sieved, make by 100 purpose samples.
Using should be by 100 purpose sample, at 170 ℃ it is solidified and makes the resin body A-Z-1 that mixes.This resin mixed, and to be ground into maximum diameter be 2～3mm size to body A-Z-1.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 60 〉
Except using anion exchange composition 1-6 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-2 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜comparative example 15 〉
Except using tMAH1 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make relatively the resin body A-H-1 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 61 〉
Except using anion exchanger 10 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-3 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 62 〉
Except using anion exchanger 11 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-4 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜comparative example 16 〉
Except using MAH1 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make relatively the resin body A-H-3 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 63 〉
Except using anion exchange composition 1-4 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-5 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 64 〉
Except using anion exchange composition 1-7 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-6 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 65 〉
Except using anion exchange composition 1-8 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-7 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 66 〉
Except using anion exchanger B-9 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-8 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 67 〉
Except using anion exchanger B-10 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-9 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 68 〉
Except using anion exchange composition 2-2 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-10 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 69 〉
Except using anion exchange composition 2-3 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-11 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 70 〉
Except using anion exchange composition 2-4 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-12 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 71 〉
Cloudy except using from substituting when making resin and mixing body A-Z-1 the employed anion exchange composition 1-5 in exchange composition 2-5 and embodiment 59 carries out same operation, make the resin body A-Z-13 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 72 〉
Except using anion exchanger B-3 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-14 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 73 〉
Except using anion exchange composition 2-1 to substitute when making resin and mix body A-Z-1 the employed anion exchange composition 1-5 and embodiment 59 carries out same operation, make the resin body A-Z-15 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜comparative example 17 〉
Except not using anion exchange composition 1-5 and embodiment 59 carry out same operation, make relatively the resin body A that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 74 〉
Following allotment is used in the composition and the anion exchange composition 1-5 of used for electronic device encapsulation material, uses mix this composite 3～5 minutes of 80 ℃～90 ℃ hot-rolling.
80 parts in cresols-novolac type epoxy resin (epoxy resin equivalent 235)
20 parts of bromination phenol-novolac type epoxy resin (epoxy resin equivalent 275)
50 parts of phenol-novolac resins (molecular weight 700～1000)
3 parts of DBU
Amine is 3 parts of silane coupling agents (3-TSL 8330)
1 part of Brazil wax
1 part of carbon black
370 parts of fused silica
2 parts of anion exchange composition 1-5
Subsequently, cooling, pulverizing obtain powder epoxy resin composition B-Z-1.Then, use 100 purposes sieve that said composition B-Z-1 is sieved, make by 100 purpose samples.
Using should be by 100 purpose sample, at 170 ℃ it is solidified and makes the resin body B-Z-1 that mixes.This resin mixed, and to be ground into maximum diameter be 2～3mm size to body B-Z-1.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 75 〉
Except using anion exchange composition 1-6 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-2 that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜comparative example 18 〉
Except using tMAH1 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-H-1 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 76 〉
Except using anion exchanger 10 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-3 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 77 〉
Except using anion exchanger 11 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-4 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 78 〉
Except using anion exchange composition 1-4 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-5 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 79 〉
Except using anion exchange composition 1-7 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-6 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 80 〉
Except using anion exchange composition 1-8 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-7 that mixes.It is similarly pulverized, make and pulverize sample.
＜comparative example 19 〉
Except using MAH1 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-H-3 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 81 〉
Except using anion exchanger B-9 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-8 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 82 〉
Except using anion exchanger B-10 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-9 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 83 〉
Except using anion exchange composition 2-2 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-10 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 84 〉
Except using anion exchange composition 2-3 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-11 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 85 〉
Except using anion exchange composition 2-4 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-12 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 86 〉
Except using anion exchange composition 2-5 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-13 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 87 〉
Except using anion exchange composition B-3 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-14 that mixes.It is similarly pulverized, make and pulverize sample.
＜embodiment 88 〉
Except using anion exchange composition 2-1 to substitute when making resin and mix body B-Z-1 the employed anion exchange composition 1-5 and embodiment 74 carries out same operation, make the resin body B-Z-15 that mixes.It is similarly pulverized, make and pulverize sample.
＜comparative example 20 〉
Except not using anion exchange composition 1-5 and embodiment 74 carry out same operation, make relatively the resin body B that mixes.It is similarly pulverized, make and pulverize sample.Use this pulverizing sample to carry out the dissolution test of chlorion.
＜embodiment 89 〉
Zero from the mix test of body extraction chlorion of resin
The resin that adds following table 8 and table 9 in polytetrafluoroethylene (PTFE) system pressure vessel respectively mixes, and body 5 restrained and pure water 50ml is also airtight, 125 ℃ of heating 100 hours.With the water taking-up, use ion chromatography analysis to be determined at the chlorine ion concentration of stripping in the water in the time of the pH of mensuration water after the cooling.These results are shown in table 8 and table 9.
[table 8]
| No. | Sample | Chlorine ion concentration (ppm) | pH |
| Embodiment 59 | The resin body A-Z-1 that mixes | 18 | 4.4 |
| Embodiment 60 | The resin body A-Z-2 that mixes | 19 | 4.4 |
| Embodiment 61 | The resin body A-Z-3 that mixes | 19 | 4.4 |
| Embodiment 62 | The resin body A-Z-4 that mixes | 19 | 4.5 |
| Embodiment 63 | The resin body A-Z-5 that mixes | 17 | 4.4 |
| Embodiment 64 | The resin body A-Z-6 that mixes | 18 | 4.4 |
| Embodiment 65 | The resin body A-Z-7 that mixes | 19 | 4.4 |
| Embodiment 66 | The resin body A-Z-8 that mixes | 18 | 4.3 |
| Embodiment 67 | The resin body A-Z-9 that mixes | 19 | 4.3 |
| Embodiment 68 | The resin body A-Z-10 that mixes | 17 | 4.5 |
| Embodiment 69 | The resin body A-Z-11 that mixes | 17 | 4.5 |
| Embodiment 70 | The resin body A-Z-12 that mixes | 18 | 4.3 |
| Embodiment 71 | The resin body A-Z-13 that mixes | 19 | 4.4 |
| Embodiment 72 | The resin body A-Z-14 that mixes | 17 | 4.5 |
| Embodiment 73 | The resin body A-Z-15 that mixes | 16 | 4.4 |
| Comparative example 15 | The resin body A-H-1 that mixes relatively | 19 | 4.4 |
| Comparative example 16 | The resin body A-H-3 that mixes relatively | 55 | 4.3 |
| Comparative example 17 | The resin body A that mixes relatively | 60 | 4.2 |
[table 9]
| No. | Sample | Chlorine ion concentration (ppm) | pH |
| Embodiment 74 | The resin body B-Z-1 that mixes | 19 | 6.8 |
| Embodiment 75 | The resin body B-Z-2 that mixes | 20 | 6.8 |
| Embodiment 76 | The resin body B-Z-3 that mixes | 41 | 6.7 |
| Embodiment 77 | The resin body B-Z-4 that mixes | 45 | 6.7 |
| Embodiment 78 | The resin body B-Z-5 that mixes | 18 | 6.8 |
| Embodiment 79 | The resin body B-Z-6 that mixes | 39 | 6.8 |
| Embodiment 80 | The resin body B-Z-7 that mixes | 40 | 6.8 |
| Embodiment 81 | The resin body B-Z-8 that mixes | 40 | 6.8 |
| Embodiment 82 | The resin body B-Z-9 that mixes | 41 | 6.7 |
| Embodiment 83 | The resin body B-Z-10 that mixes | 20 | 6.8 |
| Embodiment 84 | The resin body B-Z-11 that mixes | 20 | 6.8 |
| Embodiment 85 | The resin body B-Z-12 that mixes | 41 | 6.8 |
| Embodiment 86 | The resin body B-Z-13 that mixes | 42 | 6.7 |
| Embodiment 87 | The resin body B-Z-14 that mixes | 40 | 6.8 |
| Embodiment 88 | The resin body B-Z-15 that mixes | 18 | 6.9 |
| Comparative example 18 | The resin body B-H-1 that mixes relatively | 40 | 6.8 |
| Comparative example 19 | The resin body B-H-3 that mixes relatively | 58 | 6.8 |
| Comparative example 20 | The resin body B that mixes relatively | 62 | 6.8 |
Can know these anion exchangers from table 7, table 8 and table 9, near the ion exchange ratio height neutrality.And, also be the low material of hygroscopicity.In addition, when adding anion exchanger of the present invention in the encapsulation timber fat of electronic device etc., the pH value of potting resin extract is in slant acidity or partial neutral all has the effect of inhibition chlorion from the potting resin stripping.By this, can in relative broad range, provide reliability high encapsulation material composition.
Industrial utilizability
Anion exchanger hygroscopicity of the present invention is low and/or have good heat resistance, and near the ion exchange ratio neutral is high. In addition, allotment anion exchanger of the present invention also has the effect that suppresses the anion stripping in resin. Therefore, anion exchanger of the present invention can be used in encapsulation, coating, and the various uses such as insulation of the high electronic device of reliability or electric component on a large scale. In addition, anion exchanger of the present invention can be used in the stabilizing agent, antirust agent etc. of the resins such as vinyl chloride.
Claims (9)
1. anion exchanger, it is by using metal salt solution and/or metal alkoxide solution to handle the hydrotalcite calcined material shown in the following formula (1) and/or the hydrotalcite compound shown in the following formula (2) obtains,
M
2+ xM
3+ yO
z (1)
The M of formula (1)
2+Be Mg
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, or Zn
2+, M
3+Be Al
3+, Fe
3+, Cr
3+, Co
3+, or In
3+, x, y, z are the positive number more than 0.1,2x+3y=2z, and x〉and y, the value of x/y is below 9;
M
2+ 1-XM
3+ X(OH
-)
2(A
n-)
d·m H
2O (2)
The M of formula (2)
2+Be Mg
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+Or Zn
2+, M
3+Be Al
3+, Fe
3+, Cr
3+, Co
3+, or In
3+, An
-Be OH
-, F
-, Cl
-, Br
-, NO
3 -, CO
3 2-, SO
4 2-, Fe (CN)
6 3-, CH
3COO
-, oxalic ion or salicylic acid ion the anion of n valency, X is the positive number below 0.33 more than 0.1, m is 0 or positive number, d is X/n,
The metal of wherein said metal salt solution or metal alkoxide solution for from silicon, titanium, zirconium, tin, and aluminium select more than at least a kind.
2. anion exchanger as claimed in claim 1, wherein also allotment has magnesia.
3. a resin composition for electronic part sealing wherein contains claim 1 or 2 described anion exchangers.
4. resin composition for electronic part sealing as claimed in claim 3 wherein also contains the inorganic cation permutoid.
5. used for sealing electronic device resin, it solidifies claim 3 or 4 described resin composition for electronic part sealing and forms.
6. electronic device, it is to use claim 3 or 4 described resin composition for electronic part sealing potted elements to form.
7. a varnish, bonding agent or cream wherein contain claim 1 or 2 described anion exchangers.
8. varnish as claimed in claim 7, bonding agent or cream wherein also contain the inorganic cation permutoid.
9. the goods that contain claim 7 or 8 described varnish, bonding agent or cream.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2004/018848 WO2006064568A1 (en) | 2004-12-16 | 2004-12-16 | Anion exchanger and resin composition for electronic part sealing utilizing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101084066A CN101084066A (en) | 2007-12-05 |
| CN100518939C true CN100518939C (en) | 2009-07-29 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800446464A Expired - Fee Related CN100518939C (en) | 2004-12-16 | 2004-12-16 | Anion exchanger and resin composition for electronic part sealing utilizing the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2006064568A1 (en) |
| CN (1) | CN100518939C (en) |
| WO (1) | WO2006064568A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008056506A (en) * | 2006-08-29 | 2008-03-13 | Toda Kogyo Corp | Silicic acid-covered hydrotalcite compound particle powder, and chlorine-containing resin stabilizer and chlorine-containing resin composition using the particle powder |
| JP5463525B2 (en) * | 2008-01-31 | 2014-04-09 | 独立行政法人産業技術総合研究所 | Selective adsorbent and method for producing the same |
| KR101774624B1 (en) * | 2011-08-05 | 2017-09-04 | 세키스이가가쿠 고교가부시키가이샤 | Conductive material and connection structure |
| US11111154B2 (en) | 2012-09-28 | 2021-09-07 | Scg Chemicals Co., Ltd. | Aqueous miscible organic-layered double hydroxide |
| GB201217348D0 (en) | 2012-09-28 | 2012-11-14 | Scg Chemicals Co Ltd | Modification of layered double hydroxides |
| GB201405543D0 (en) | 2014-03-27 | 2014-05-14 | Isis Innovation | High surface area layered double hydroxides |
| JP6246050B2 (en) * | 2014-04-14 | 2017-12-13 | オリンパス株式会社 | Resin composition, backing material for ultrasonic vibrator, ultrasonic vibrator, and ultrasonic endoscope |
| JP2017168808A (en) * | 2015-11-06 | 2017-09-21 | 株式会社カネカ | Thermosetting white ink for CSP-LED |
| CN109266228B (en) * | 2018-08-20 | 2020-11-13 | 河北省同创交通工程配套产品产业技术研究院 | Super-strong chemical reaction type high-molecular self-adhesive rubber water stop belt and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57192410A (en) * | 1981-05-22 | 1982-11-26 | Showa Denko Kk | Production of ethylene polymer |
| JPH0687982B2 (en) * | 1989-06-21 | 1994-11-09 | 東亞合成化学工業株式会社 | Granular inorganic ion exchanger |
| JP3563798B2 (en) * | 1993-12-24 | 2004-09-08 | ライオン株式会社 | Method for producing fatty acid polyoxyalkylene alkyl ether |
| JPH08313919A (en) * | 1995-05-19 | 1996-11-29 | Toagosei Co Ltd | Resin composition for liquid crystal sealing material |
| JPH10167706A (en) * | 1996-12-09 | 1998-06-23 | Oji Yuka Synthetic Paper Co Ltd | Compound inorganic fine powder and it utilization |
| JP2000049259A (en) * | 1998-05-29 | 2000-02-18 | Hitachi Chem Co Ltd | Sealing epoxy resin molding material and electronic part |
| JP4332691B2 (en) * | 1999-02-05 | 2009-09-16 | 戸田工業株式会社 | Method for producing Mg-Al hydrotalcite type particle powder, chlorine-containing resin stabilizer and Mg-Al type hydrotalcite type particle powder |
| JP2002080566A (en) * | 2000-07-04 | 2002-03-19 | Sumitomo Bakelite Co Ltd | Epoxy rein composition and semiconductor device |
| JP4429566B2 (en) * | 2002-02-08 | 2010-03-10 | 戸田工業株式会社 | Agricultural film heat insulating agent, agricultural film masterbatch pellets and agricultural film |
| JP4337411B2 (en) * | 2003-06-09 | 2009-09-30 | 東亞合成株式会社 | Inorganic anion exchanger and epoxy resin composition for sealing electronic parts using the same |
-
2004
- 2004-12-16 WO PCT/JP2004/018848 patent/WO2006064568A1/en not_active Application Discontinuation
- 2004-12-16 JP JP2006548622A patent/JPWO2006064568A1/en active Pending
- 2004-12-16 CN CNB2004800446464A patent/CN100518939C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2006064568A1 (en) | 2008-06-12 |
| CN101084066A (en) | 2007-12-05 |
| WO2006064568A1 (en) | 2006-06-22 |
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