CN101085868B - Resin composition based on polyimide siloxane - Google Patents
Resin composition based on polyimide siloxane Download PDFInfo
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- CN101085868B CN101085868B CN2007101099194A CN200710109919A CN101085868B CN 101085868 B CN101085868 B CN 101085868B CN 2007101099194 A CN2007101099194 A CN 2007101099194A CN 200710109919 A CN200710109919 A CN 200710109919A CN 101085868 B CN101085868 B CN 101085868B
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Nc1ccccc1 Chemical compound Nc1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 0 [O-][N+](*12[N+]([O-])O[N+]1[O-])O[N+]2[O-] Chemical compound [O-][N+](*12[N+]([O-])O[N+]1[O-])O[N+]2[O-] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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Abstract
This invention relates to a resin composition based on polyimide silicone. The said composition comprises (a) Polyamic acid which is a resultant of a tetracarboxylic acid compound, aromatic diamine, and a diamino siloxane which are chosen from a group which comprises an aromatic tetracarboxylic acid compound and an alicyclic tetracarboxylic acid compound, And polymer chosen from a group which comprises polyimide silicone which is a ring closure derivative of this polyamic acid, (b) a solvent; and (c) reactive-silyl-groups diimide compound with imide ring derivated from diimide compound containing phenolic hydroxyl group and alkoxyl silyl group. The said composition is used for electrode protective material to prevent the surface of the electrode from corroding and display excellent binding to the basis material.
Description
Technical field
The present invention relates to be suitable in electronic package, to be used as the electrode protection material based on the resin combination of Polyimidesiloxane and also relate to the electrode protection material that comprises such composition.
Background technology
Polyimide resin, its shows excellent thermotolerance and outstanding electricity and mechanical property, is widely used as the resin of the insulating protective film that forms electronic package etc. usually.During the formation of these protective membranes; because polyimide resin is insoluble to organic solvent usually; adopt a kind of method; this method is used the solution of polyamic acid; polyamic acid is the precursor of polyimide resin; with this solution is applied to base material and heating then, therefore cause closed loop by dehydration condensation and form the coating of target polyimide resin.
Yet, in using these polyamic acid solutions, there is variety of issue, comprise that polyamic acid solution has very high viscosity and therefore has poor processability, the polyimide resin coating that requires to surpass 300 ℃ high temperature and obtain during the dehydrating condensation process shows bonding to the difference of base material such as nickel, aluminium, silicon and silicon oxide film.
For improving these problems relevant with conventional polyimide, propose to use the method for Polyimidesiloxane, comprise that by employing the part that the diamine of siloxane structure replaces as a kind of diamine component of polyimide starting material obtains Polyimidesiloxane (referring to references 1 and references 2).Polyimidesiloxane is widely used in electronics and electrical industry, as the surface protection film of electronic package with as the interbed insulating material of electronic package and other heat-resistant components.By applying or form pattern process, Polyimidesiloxane is used for the surface of covering substrates.These Polyimidesiloxanes are in conjunction with derived from the high heat resistance level of polyimide structures with derived from the low elastic modulus of siloxane structure, but has higher moisture permeable level owing to compare them with the polyimide that does not comprise siloxane structure, moisture can more easily reach the interface between electrode and Polyimidesiloxane, if comprise ionic impurity with water, then but the corrosion of generating electrodes causes integrity problem.In addition, aspect the level of adhesion of base material, still require other improvement at these Polyimidesiloxanes.
Above problem for the existence that solves by ionic impurity causes proposes a kind of method, and the Polyimidesiloxane that wherein contains ion exchange resin or inner complex resin is as undercoat resin (referring to references 3).By using this method, be hunted down as the ionic impurity in the epoxy resin layer of external coating (EC) resin, mean do not have ion reach semiconductor surface near, the result is, can stably and have the high voltage diode of high-voltage and low electric leakage with high yield manufacturing.Yet, under the hot conditions of using during the durability test, above clearly ion exchange resin or inner complex resin self decompose and since then ion be present in electrode surface, generating electrodes corrosive problem again.In addition, because ion exchange resin swelling in the presence of solvent, it is dissatisfied that the solvent removal that carries out during aftertreatment makes us easily, and this causes the remarkable reduction of physical strength of resin and the deterioration of electrical property.
[references 1] JP 43-27439B
[references 2] JP 59-7213B
[references 3] JP 10-294319A
Summary of the invention
Therefore, the purpose of this invention is to provide the resin combination based on Polyimidesiloxane, said composition is suitable for use as the electrode protection material, prevents in the corrosion of electrode surface and shows excellent bonding to base material.
The double imide compound that the new reaction that the present inventor finds to contain imide ring and alkoxysilyl contains silyl can at room temperature solidify, show excellent workability, with can form the solidified coating that comprises the imide ring structure, this coating shows excellent thermotolerance, physical strength and electrical property.They find that also this solidified coating shows the excellent bonding and excellent solvent resistance to base material, so are used as the material of the protective membrane of formation electronic package etc. ideally.
In addition, the inventor also finds by contain the double imide compound and the Polyimidesiloxane resin of silyl in conjunction with above reactivity, can improve coating based on Polyimidesiloxane to the bonding of base material with can obtain to prevent at the corrosive of electrode surface resin combination based on Polyimidesiloxane.According to the result of the further investigation of these discoveries, the inventor can finish the present invention.
In other words, a first aspect of the present invention provides the resin combination based on Polyimidesiloxane, and said composition comprises:
(a) be selected from following polymkeric substance: polyamic acid, it is the tetracarboxylic compound that is selected from aromatic acid's compound and alicyclic tetracarboxylic compound, and the reaction product of aromatic diamine and diamino siloxanes; With the Polyimidesiloxane of representing these polyamic acid closed loop derivatives;
(b) solvent; With
(c) reactivity of being represented by the structural formula (1) of following demonstration contains the double imide compound of silyl:
(wherein, X represents quadrivalent organic radical group, R
1And R
2The identical or different not replacement of 1-10 carbon atom of expression or replacement univalence hydrocarbyl and m represent integer 1-20).
A second aspect of the present invention provides the electrode protection that comprises above composition material.
A third aspect of the present invention provides the method for the cured product guard electrode that adopts above composition, and this method comprises the steps:
Apply composition to electrode and
Curing composition is to form cured product on the top of electrode.
A fourth aspect of the present invention provides the film of the cured product that comprises above composition.
A fifth aspect of the present invention provides the production method of the film of the cured product that comprises above composition, and this method comprises the steps:
Apply composition to base material and
Curing composition is to form cured product on the top of base material.
Because the resin combination based on Polyimidesiloxane of the present invention comprises the double imide compound that above-mentioned reactivity contains silyl, the coating that forms from composition shows the favourable bond strength to base material, can prevent based on the cold coating of Polyimidesiloxane and the corrosion at the interface between the electrode, even under the voltage that is applying during the durability test, also not corrode at electrode surface.Therefore, composition of the present invention is suitable for electrode protection ideally to be used, as the formation of electrode protection material.
Following is detailed description of the present invention.
[(a) polymkeric substance]
[tetracarboxylic compound]
Be used for " being selected from the tetracarboxylic compound of aromatic acid's compound and alicyclic tetracarboxylic compound " of the present invention and comprise tetracarboxylic acid and its derivative such as (hereinafter referred to as " tetracarboxylic acid components ") such as monoester anhydride, dicarboxylic anhydride, monoesters and diester.
The object lesson of preferred tetracarboxylic acid component comprises pyromellitic acid dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dicarboxylic anhydride, 2,3,3 ', 4 '-the biphenyltetracarboxyacid acid dicarboxylic anhydride, 3,3 ', 4,4 '-the biphenyltetracarboxyacid acid dicarboxylic anhydride, 1,3-two (3,4-dicarboxyl phenyl)-1,1,3,3-tetramethyl disiloxane dicarboxylic anhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-ditan tetracarboxylic acid dicarboxylic anhydride, 1, two (3,4-dicarboxyl phenyl) the ethane dicarboxylic anhydrides of 1-, 3,3 ', 4,4 '-(2, the 2-diphenyl propane) tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-(2,2-phenylbenzene HFC-236fa) tetracarboxylic acid dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 1,4-two (3, the 4-di carboxyl phenyloxy) phthalic acid, it is two that [4-(3, the 4-di carboxyl phenyloxy) phenyl] the methane dicarboxylic anhydride, 1, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the ethane dicarboxylic anhydrides of 1-, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dicarboxylic anhydride, 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the HFC-236fa dicarboxylic anhydrides of 2-, tetramethylene tetracarboxylic acid dicarboxylic anhydride, and dicyclo [2.2.2] suffering-7-alkene-2,3,5,6-tetracarboxylic acid dicarboxylic anhydride; And reactive derivatives such as the ester and the diester of the tetracarboxylic acid corresponding and these tetracarboxylic acids with above tetracarboxylic acid dicarboxylic anhydride.These tetracarboxylic acid components can be used separately, or being used in combination with two or more different componentss.
[aromatic diamine]
The object lesson that is used for preferred aromatic diamine of the present invention comprises 4; 4 '-diaminodiphenyl-methane; adjacent-; between-and p-phenylenediamine; two [4-(3-amino-benzene oxygen) phenyl] sulfone; 2; the 4-diaminotoluene; 2; the 5-diaminotoluene; 2; 4-diamino dimethylbenzene; 3; 6-diamino durene; 2; 2 '-dimethyl-4; 4 '-benzidine; 2; 2 '-diethyl-4; 4 '-benzidine; 2; 2 '-dimethoxy-4 '; 4 '-benzidine; 2; 2 '-diethoxy-4; 4 '-benzidine; 4; 4 '-diaminodiphenyl oxide; 3; 4 '-diaminodiphenyl oxide; 4; 4 '-diamino diphenyl sulfone; 3; 3 '-diamino diphenyl sulfone; 4; 4 '-the diamino benzophenone; 3; 3 '-the diamino benzophenone; 1; two (3-amino-benzene oxygen) benzene of 3-; 1; two (4-amino-benzene oxygen) benzene of 3-; 1; two (4-amino-benzene oxygen) benzene of 4-; 4; 4 '-two (4-amino-benzene oxygen) biphenyl; two [4-(4-amino-benzene oxygen) phenyl] sulfone; 2; two [4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2; two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-; 2; two [4-(3-amino-benzene oxygen) phenyl] propane of 2-; 2; two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-; 2; two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa of 2-; 2; two [4-(3-amino-5-4-trifluoromethylphenopendant) phenyl] HFC-236fa of 2-; 2; two (4-aminophenyl) HFC-236fa of 2-; 2; two (3-aminophenyl) HFC-236fa of 2-; 2; two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-; 2; two (3-amino-4-aminomethyl phenyl) HFC-236fa of 2-; 4; 4 '-two (4-amino-benzene oxygen) octafluoro biphenyl; 2; 2 '-two (trifluoromethyl)-4; 4 '-benzidine; 3; 5-diamino benzo trifluoride; 2; 5-diamino benzo trifluoride; 3; 3 '-two (trifluoromethyl)-4,4 '-benzidine; 3,3 '-two (trifluoromethyl)-5; 5 '-benzidine; 1; 4-two (the amino tetrafluoro phenoxy group of 4-) tetra fluoro benzene; 4,4 '-two (the amino tetrafluoro phenoxy group of 4-) octafluoro biphenyl; 4,4 '-the diamino dinaphthalene; with 4,4 '-diamino N-benzanilide.These compounds can use separately, or use with two or more different combination of compounds.
[diamino siloxanes]
The object lesson that is used for preferred diamino siloxanes of the present invention comprises 1, two (the 3-aminopropyls)-1,1 of 3-, 3,3-tetramethyl disiloxane, 1, two (the amino butyl of 4-)-1 of 3-, 1,3,3-tetramethyl disiloxane, two (4-amino-benzene oxygen) dimethylsilane and 1, two (the 4-amino-benzene oxygens)-1 of 3-, 1,3,3-tetramethyl disiloxane and the compound of representing by the general formula (2) of following demonstration:
H
2N-Z-(SiR
2O)
m-SiR
2-Z-NH
2 (2)
(wherein, each R represents the not replacement of 1-10 carbon atom independently or replaces monovalent hydrocarbon, preferably do not comprise the univalence hydrocarbyl of 1-8 carbon atom of aliphatic unsaturated group or the cycloalkyloxy of alkoxyl group, alkene oxygen base or 1-8 carbon atom; Each Z represents the not replacement of 1-8 carbon atom or replaces bivalent hydrocarbon radical that it can comprise the ehter bond Sauerstoffatom in the chain independently; Represent integer 1-100 with m, preferred 3-60).
These diamino siloxanes can use separately, or use with two or more different combination of compounds.
In above general formula (2), R represents that under those situations of univalence hydrocarbyl, the suitable example of R comprises alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, heptyl or octyl group therein; Thiazolinyl such as vinyl, allyl group, propenyl, pseudoallyl, butenyl, isobutenyl or hexenyl; Cycloalkyl such as cyclopentyl or cyclohexyl; Cycloalkenyl group such as cyclohexenyl; Aryl such as phenyl, tolyl or xylyl; Aralkyl such as benzyl, ethylphenyl or propyl group phenyl; Wherein at least one hydrogen atom in these alkyl is by halogen atom such as fluorine atom, chlorine atom or bromine atoms, or the group that is replaced by cyano group, as chloromethyl, 3-fluoropropyl, 3,3, and 3-trifluoro propyl, 4-fluorophenyl or 2-cyano ethyl.
In addition, R represents that under those situations of alkoxyl group, alkene oxygen base or cycloalkyloxy, the suitable example of R comprises methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, hexyloxy, cyclohexyloxy, octyloxy, vinyloxy group, allyloxy, propenyloxy group or different propenyloxy group therein.
In above general formula (2), the example that can comprise two bivalent hydrocarbon radicals being represented by Z of ehter bond Sauerstoffatom in the chain comprises alkylidene group such as methylene radical, ethylidene, propylidene (trimethylene), (condition is to form 2-amino-1-methylethyl on amino bonded to the two methyl ethylidene to the methyl ethylidene, perhaps on amino bonded to the two methyl ethylidene to form the 2-aminopropyl), tetramethylene, 2-methyl propylidene, (condition is to form 3-amino-1-methyl-propyl on amino bonded to the two methyl propylidene to 1-methyl propylidene, perhaps on amino bonded to the two methyl propylidene to form the amino butyl of 3-), (condition is to form 1-(amino methyl) propyl group on amino bonded to the two ethyl ethylidene to the ethyl ethylidene, perhaps on amino bonded to the two ethyl ethylidene to form the amino butyl of 2-), hexa-methylene, or eight methylene radical; Arylidene as adjacent-,-or right-phenylene or methylene phenyl; With alkylidene group-arylidene of being represented by the general formula of following demonstration, it can comprise the ehter bond Sauerstoffatom.
(wherein, the phenyl ring of amino bonded in three general formulas of above demonstration)
Comprise the compound of following demonstration by the object lesson of the diamino siloxanes of above general formula (2) expression, although this is not a restrictive list.
(wherein, m is the integer of 3-60)
(wherein, m is the integer of 3-60)
The usage quantity of diamino siloxanes is preferred enough to make based on the quantity of the structure of the diamino siloxanes in the Polyimidesiloxane of the closed loop derivative of polyamic acid or expression polyamic acid the polyamic acid unit or the unitary quantity of closed loop polyimide of the generation of the reaction between tetracarboxylic compound and the diamino siloxanes (promptly by), with respect to all repeating units that constitute polyamic acid or Polyimidesiloxane in conjunction with total amount, be 1-60mol%, even more preferably 5-60mol% and most preferably 10-50mol%.If the quantity of diamino siloxanes in this scope, is given snappiness to resin combination easilier, can suppress the increase and the stable on heating level of easier maintenance of moisture permeable.In other words, with respect to the total moles order of aromatic diamine and diamino siloxanes, the quantity of diamino siloxanes is preferably 1-60mol%, even more preferably 5-60mol% and most preferably 10-50mol%.
[(b) solvent]
The solvent of component (b) is for having excellent solvent solvent, as synthetic solvent of typically being used for polyamic acid etc.The example of preferred solvent comprises N-Methyl pyrrolidone; Straight chain or cyclic amide based solvent such as N, dinethylformamide and N,N-dimethylacetamide; Lactone such as gamma-butyrolactone, Alpha-Methyl-gamma-butyrolactone, γ-Wu Neizhi, δ-Wu Neizhi, γ-Ji Neizhi, and 6-caprolactone; Carbonic ether such as propylene carbonate; Ester such as butylacetate, cellosolve acetate ethyl ester and cellosolve acetate butyl ester; Ether such as dibutyl ether, diethylene glycol dimethyl ether and triglycol dimethyl ether; Cyclic ether such as tetrahydrofuran (THF); Ketone such as methyl iso-butyl ketone (MIBK), pimelinketone, and methyl phenyl ketone; Alcohol is as butanols, octanol, and ethyl cellosolve (ethyl cellosolve); And the urea groups solvent, sulfoxide group solvent such as methyl-sulphoxide, sulfone kind solvent, varsol such as toluene and halogen radical solvent such as chloroform and tetracol phenixin.These solvents can use separately, or being used in combination with two or more different solvents.
Usage quantity for this solvent does not have specific restriction, although preferably do not influence the quantity based on the stability of the resin combination of Polyimidesiloxane.Typically, the quantity of solvent is preferably 50-1,900 mass parts and even more preferably 100-900 mass parts, per 100 mass parts components (a).
[(c) reactivity contains the double imide compound of silyl]
Being used for the double imide compound that reactivity of the present invention contains silyl generates by reacting following material: by the aniline of the phenolic hydroxy group of structural formula shown below (3) expression:
(wherein, R
1Represent 1-10 carbon atom, preferred 1-6 carbon atom, even the more preferably identical or different not replacement or the replacement univalence hydrocarbyl of 1-3 carbon atom),
With two sense acid anhydrides by structural formula shown below (4) expression:
(wherein, X represents quadrivalent organic radical group and preferably has the quadrivalent organic radical group of aromatic ring structure and be selected from the quadrivalent organic radical group of the quadrivalent organic radical group that is represented by general formula shown below especially) reaction,
Therefore form double imide compound by the phenolic hydroxy group of structural formula shown below (5) expression:
(wherein, X and R
1As defined above) and subsequently the double imide compound of this phenolic hydroxy group is carried out and dealcoholization condensation reaction by the organic silane compound that comprises the alkoxyl group that is bonded to Siliciumatom of general formula (6) expression shown in above:
(wherein, R
2Group is represented 1-10 carbon atom, preferred 1-6 carbon atom, even more preferably the identical or different not replacement of 1-3 carbon atom or replacement univalence hydrocarbyl and m represent integer 1-20, preferably 1-12),
Therefore obtain compound by general formula shown below (1) expression:
(wherein, X, R
1, R
2And m as defined above).
Below be provided for preparing above reactivity and contain the starting material of double imide compound of silyl and the more detailed description of production method.
The aniline of＜phenolic hydroxy group 〉
In the aniline of the phenolic hydroxy group of representing by structural formula shown below (3):
(wherein, R
1As defined above),
Phenolic hydroxyl group can replace any hydrogen atom that is bonded to the carbon atom of phenyl ring skeleton in the above general formula (3).In addition, the aniline of phenolic hydroxy group can be the simplification compound, or has the combination of two or more isomer of different the position of substitution of phenolic hydroxyl group.
＜two sense acid anhydrides 〉
In two sense acid anhydrides by structural formula shown below (4) expression:
(wherein, X represents quadrivalent organic radical group),
Radicals X preferably has the quadrivalent organic radical group of aromatic ring structure.The object lesson of organic group is as follows, although this is not restrictive tabulation.
In addition, the example of other two senses acid anhydrides comprises 2,3,3 ', 4 '-the biphenyltetracarboxyacid acid dicarboxylic anhydride, 1,3-two (3,4-dicarboxyl phenyl)-1,1,3,3-tetramethyl disiloxane dicarboxylic anhydride, 3,3 ', 4,4 '-ditan tetracarboxylic acid dicarboxylic anhydride, 1, two (3,4-dicarboxyl phenyl) the ethane dicarboxylic anhydrides of 1-, 3,3 ', 4,4 '-(2, the 2-diphenyl propane) tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-(2,2-phenylbenzene HFC-236fa) tetracarboxylic acid dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 1,4-two (3, the 4-di carboxyl phenyloxy) phthalic acid, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] methane dicarboxylic anhydride, 1,1-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the ethane dicarboxylic anhydride, 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dicarboxylic anhydrides of 2-, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the HFC-236fa dicarboxylic anhydride, tetramethylene tetracarboxylic acid dicarboxylic anhydride, and dicyclo [2.2.2] suffering-7-alkene-2,3,5,6-tetracarboxylic acid dicarboxylic anhydride.These compounds can use separately, or use with two or more different combination of compounds.
The preparation of the double imide compound of＜phenolic hydroxy group 〉
Adopt the mode similar to conventional synthetic method, wherein polyamic acid is prepared from tetracarboxylic acid and diamine compound, carry out closed loop then to form polyimide, the aniline of above phenolic hydroxy group and above two sense acid anhydrides one are reacted in organic solvent, obtain the intermediate of representing by structural formula shown below:
(wherein, X and R
1As defined above),
With with this intermediate by under heating, carrying out dehydrating condensation and carry out closed loop subsequently, therefore obtain double imide compound by the phenolic hydroxy group of structural formula shown below (5) expression:
(wherein, X and R
1As defined above).
＜reactivity contains the preparation of the double imide compound of silyl 〉
With the double imide compound of above phenolic hydroxy group with comprise the organic silane compound of the alkoxyl group that is bonded to Siliciumatom by general formula shown below (6) expression:
(wherein, R
2With m as defined above)
In the presence of condensation catalyst, use normal method and in solvent such as toluene, methyl iso-butyl ketone (MIBK) or tetrahydrofuran (THF), carry out dealcoholization, therefore at phenolic hydroxyl group be bonded between the alkoxyl group of Siliciumatom and cause dealcoholization condensation reaction, it obtains as component of the present invention (c), is contained the double imide compound of silyl by the reactivity of general formula (1) expression:
(wherein, X, R
1, R
2With m as defined above).
In organic silane compound by above general formula (1) expression, radicals R
1And R
2Suitable example comprise alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, nonyl or decyl; Cycloalkyl such as cyclopentyl or cyclohexyl; Aryl such as phenyl, methylbenzene, xylyl or naphthyl; Aralkyl such as benzyl, styroyl or phenyl propyl; Haloalkyl such as chloromethyl, 3-chloropropyl, 3-fluoropropyl or 3,3, the 3-trifluoro propyl; With thiazolinyl such as vinyl, allyl group, propenyl, pseudoallyl, butenyl, isobutenyl, pentenyl or hexenyl.In these, preferably do not comprise the group of aliphatic unsaturated link(age), even to be more preferably alkyl and to wish most be methyl or ethyl.
Dealcoholization self is well-known in the art, and the usage quantity of key element such as condensation catalyst and reaction conditions can be set according to typical method.The example of condensation catalyst comprises conventional condensation catalyst, and object lesson comprises titaniferous organic compound such as tetraisopropoxy titanium, four titanium butoxide, two (methyl ethyl diketone) titanium and titanium chelate compound; Highly basic such as tetramethyl guanidine and tetramethyl-guanidine radicals propyl trimethoxy silicane; With metal carboxylate such as zinc octoate, 2 ethyl hexanoic acid lead, dibutyltin diacetate, lactyl-lactic acid dibutyl tin, two sad dibutyl tins, stannous octoate, zinc naphthenate and sad ferrous.In these, tin class catalyzer preferably.These catalyzer can use separately, or being used in combination with two or more different catalysts.
Component of the present invention (c) can be used the simplification compound, or two or more different combination of compounds.
The usage quantity of component (c) is preferably the 5-200 mass parts, even more preferably 10-100 mass parts, per 100 mass parts components (a).If this quantity is in above scope; the coating that forms from composition of the present invention can not be brittle; also show favourable bonding to base material; mean that composition not only can be advantageously used for the protecting materials of the electrode that comprises hard base material, and be used as the protecting materials of the electrode that comprises flexible parent metal.
[preparation of compositions]
The synthetic of the polyamic acid of component (a) or Polyimidesiloxane (the closed loop derivative of polyamic acid) undertaken by following mode: adopt molal quantity hybrid diamine component and tetracarboxylic acid components such as basic in reaction vessel, by heating in solvent two kinds of components one are reacted then.In preferred synthetic, will disperse or dissolve in the solvent of diamine components in reaction vessel, then at low temperatures and under constant agitation, drip the solution or the dispersion of tetracarboxylic acid component, the mixture that obtains of heating then.
Be to obtain polyamic acid, the temperature condition that uses during reacting by heating typically is 5-100 ℃, preferred 20-80 ℃, for the diamine components of 100g and tetracarboxylic acid component in conjunction with quantity, heating was typically carried out about 1-24 hour.In addition, for obtaining the basic Polyimidesiloxane of imidization fully, for the diamine components of 100g and tetracarboxylic acid component in conjunction with quantity, reacting by heating is carried out about 1-24 hour time typically at 120-200 ℃ under preferred 140-180 ℃ the temperature.Under 120 ℃ or lower temperature, slow to imido conversion rate, although can use 200 ℃ or higher temperature, they do not provide specific benefit.
The double imide compound that the reactivity of component (c) contains silyl adds after above reacting by heating is finished.
In preferred embodiments, different with above-mentioned object lesson, will be by the diamino siloxanes of 10-15mol% by general formula shown below (2) expression:
H
2N-Z-(SiR
2O)
m-SiR
2-Z-NH
2 (2)
(wherein, R, Z, with m as defined above) and the diamine components formed of two [4-(4-amino-benzene oxygen) phenyl] sulfones of 85-90mol%, adopt molal quantities such as basic with the tetracarboxylic acid component of forming by 50-80mol% pyromellitic acid dicarboxylic anhydride and 20-50mol% benzophenone tetracarboxylic acid dicarboxylic anhydride, at pimelinketone, one reacts to produce the resin solid fraction concentration of 30-45 quality % in the solvent of the sufficient amount of gamma-butyrolactone or N-Methyl pyrrolidone, therefore produce the Polyimidesiloxane of imidization substantially fully, with after this reaction is finished, the answering property that adds component (c) contains the double imide compound of silyl.
[other component]
Except that said components (a)-(c), composition of the present invention also can comprise the component that other is optional, and condition is the performance that the adding of these other components does not damage composition of the present invention.
The double imide compound that the reactivity of component of the present invention (c) contains silyl comprises condensation reaction group such as alkoxyl group or alkene oxygen base at two ends, the result is that conventional condensation catalyst preferably adds the curing reaction that is undertaken by the condensation reaction between the molecule of component (c) to promote.The suitable example of this condensation catalyst comprises titaniferous organic compound such as tetraisopropoxy titanium, four titanium butoxide, two (methyl ethyl diketone) titanium and titanium chelate compound; Highly basic such as tetramethyl guanidine and tetramethyl-guanidine radicals propyl trimethoxy silicane; With metal carboxylate such as zinc octoate, 2 ethyl hexanoic acid lead, dibutyltin diacetate, lactyl-lactic acid dibutyl tin, two sad dibutyl tins, stannous octoate, zinc naphthenate and sad ferrous.These catalyzer can use separately, or being used in combination with two or more different catalysts.If use condensation catalyst, then the quantity to catalyzer does not have specific restriction, and it only needs is effective catalytic quantity, although with respect to 100 mass parts said components (c), typical quantity is preferably the 0.01-6.0 mass parts, even more preferably 0.05-5.0 mass parts.
[paint film]
After being applied to the resin combination based on Polyimidesiloxane of the present invention on the base material, film forming, crosslinked and curing is all undertaken by removing solvent from composition simply.The condition of this solvent removal depends on the thickness of coating and changes, but typically, and heating is used baking oven or hot plate etc. in air or under the inert atmosphere of nitrogen etc., carry out about 1-150 minute time under 20-150 ℃.Temperature condition can keep constant in entire treatment in the cycle, or can be in above temperature range elevated temperature gradually.
In addition, component (a) is that roasting can be carried out after film forming under those situations of the polyamic acid of incomplete imidization or Polyimidesiloxane therein, therefore causes ring-closure reaction and forms the basic Polyimidesiloxane of imidization fully.The condition of this roasting depends on the thickness of coating and changes but typically, uses baking oven or hot plate etc., and preferred 20 minutes-3 hours time was carried out in heating about 10 minutes-5 hours under 150-400 ℃.
Under the condition of using during above solvent removal and the film process, with under above roasting condition, the double imide compound that the reactivity of component (c) contains silyl is undertaken crosslinked by the above-mentioned condensation reaction that takes place between the molecule of component (c) and curing.
The film thickness based on the coating of Polyimidesiloxane that obtains like this is preferably 5-250 μ m, even more preferably 5-200 μ m and most preferably 10-100 μ m.
Base material is not had specific restriction, and suitable substrates comprises organic substrate, and this organic substrate comprises polyimide or BT resin; Metal such as aluminium, copper, silicon, its alloy or stainless steel; Pottery is as aluminum oxide, glass, borosilicate glass, quartz, zirconium white, mullite or silicon nitride; With semiconductor material such as barium titanate, Lithium niobium trioxide, tantalum niobate, gallium arsenide or indium phosphide.In addition, the resin combination based on Polyimidesiloxane of the present invention also can be applied to the base material that is formed by following mode: adopt thermally stable polymer compound such as polyimide, aromatic poly, polyphenylene, poly-inferior dimethylbenzene, polyphenylene oxide, polysulfones, polyamidoimide, polyester-imide, polybenzimidazole, polyquinazoline dione or polybenzoxazinone to apply on the surface of above a kind of base material.
[purposes]
The concrete purposes of the resin combination based on Polyimidesiloxane of the present invention comprises the protective membrane that is used for various purposes, as interlayer insulating film, surface protection film or α-ray shield film.These films can be applied to monolithic IC such as DRAM, SRAM or CPU, and they are installed on the base material that comprises silicon wafer or gallium arsenide etc.; Being applied to device wraps as the multicore sheet high-density of mixing IC, thermal head, image sensor or form on ceramic base material or glass baseplate etc.; Or be applied on any various wiring board such as TAB band, flexible parent metal or the solid wiring board.
Embodiment
Embodiment
Below be based on a series of synthetic embodiment, embodiment and Comparative Examples to more detailed description of the present invention, although the present invention is never by following embodiment restriction.
[synthetic embodiment 1]
To the assembling thermopair, agitator, with add 3 of 19.45g in the separable flask of glass 4-neck of reflux exchanger, 3 ', 4,4 '-sulfobenzide tetracarboxylic acid dicarboxylic anhydride (DSDA) (when the bond quality of all tetracarboxylic acid components and diamine components is considered to 100mol%, equaling 25mol% (adopting similar mode to calculate subsequently mol%)), 24.11g (25mol%) 3,3 ', 4,4 '-(2,2-phenylbenzene HFC-236fa) tetracarboxylic acid dicarboxylic anhydride (6FDA), the diamino polysiloxane that 36.55g (20mol%) is represented by general formula shown below (8):
H
2N-CH
2CH
2CH
2-[Si (CH
3)
2O]
9-Si (CH
3)
2-CH
2CH
2CH
2-NH
2(8) (name of product: KF-8010, the Shin-Etsu Chemical Co. of manufacturers, Ltd.), 13.37g (15mol%) 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-, and 6.52g (15mol%) 4 (ODA), therefore guarantee diamine components and tetracarboxylic acid component etc. molal quantity.Add the 300g pimelinketone then, mixture was stirred 4 hours down at 180 ℃ under heating, therefore obtain comprising the composition of Polyimidesiloxane and solvent.(unit of numeral is a gram to the usage quantity of table 1 demonstration composition and diamine components and tetracarboxylic acid component, and mol% numerical value shows in parenthesis.This also is applicable to table subsequently).
[synthetic embodiment 2-5]
As shown in table 1, except that the usage quantity that changes composition and diamine components and tetracarboxylic acid component, the composition that comprises Polyimidesiloxane and solvent adopts the mode identical with synthesizing embodiment 1 to prepare.
[table 1]
[synthetic embodiment 6]
(1) to the assembling agitator, the flask of thermometer and nitrogen switching equipment adds 31.02g (0.1mol) 4,4-oxydiphthalic anhydride and as the 132.13g pimelinketone of solvent.Under constant agitation, adopt the dropping mode to add gradually to comprise 21.83g (0.2mol) p-aminophenol then and as the solution of the 132.13g pimelinketone of solvent.After being added dropwise to complete, the reaction mixture that obtains was at room temperature stirred other 4 hours, the reflux exchanger of assembling moisture receptor is connected to flask, add 26.43g toluene, the temperature of reaction system is elevated to 160 ℃ and remained on this temperature following 2 hours.Subsequently, temperature is elevated to 175 ℃, remained on that temperature other 4 hours.The water number amount that produces from reaction is 3.6g.
Little reddish-brown reaction soln cool to room temperature that will obtain so then under reduced pressure removes and desolvates, and obtains double imide compound shown below.
The measurement of the infrared absorption spectrum of double imide compound is presented at 1768cm
-1From the absorption of imide bond with at 1360cm
-1The absorption from phenolic hydroxyl group.In addition, NMR spectrum is presented at the peak from phenolic hydroxyl group of 9.3ppm.
(2) the above double imide compound of 50g (0.095mol) is dissolved in the 200g methyl iso-butyl ketone (MIBK) again, temperature is raise to be removed with the azeotropic that carries out water.Add poly-(the tetramethoxy-silicane) (name of product: MS-51 of 43g to the solution that obtains, the Tama Chemicals Co. of manufacturers, Ltd., the repeating unit average number: 4) and 0.1g as the dibutyl tin laurate of catalyzer, use water separator under nitrogen gas stream, under 100 ℃, to carry out separating methanol reaction 1 hour then.Subsequently, adopt reflux exchanger to replace water separator, be reflected at 100 ℃ and continue 3 hours down, therefore obtain containing the double imide compound of methoxy methyl silylation.
This measurement of infrared absorption spectrum that contains the double imide compound of methoxy methyl silylation is presented at 1086cm
-1The absorption from the SiO key at place, and from the absorption (1360cm of phenolic hydroxyl group
-1) disappear.In addition, the announcement of NMR spectrum also disappears from the peak (9.3ppm) of phenolic hydroxyl group.
[synthetic embodiment 7 and 8]
As shown in table 2, except that the quantity that changes component described in composition and the above synthetic embodiment 6, the double imide compound that will contain the methoxy methyl silylation adopts the mode identical with synthesizing embodiment 6 to synthesize.
[table 2]
＜embodiment 1-10 〉
Use combination and the quantity (mass parts) shown in table 3 and the table 4 to be blended in the composition that comprises Polyimidesiloxane and solvent for preparing among the above synthetic embodiment 1-5, the double imide compound that contains the methoxy methyl silylation for preparing among the more than synthetic embodiment 6-8 and as the tetraisopropoxy titanium of condensation catalyst: Ti (O-iPr)
4, fully stir the mixture that obtains, therefore obtain the resin combination based on Polyimidesiloxane of the present invention.
Subsequently, use every kind of performance of following test evaluation embodiment 1-10 based on the resin combination of Polyimidesiloxane.
[bond strength measurement]
To be applied to glass baseplate based on the resin combination of Polyimidesiloxane and under 23 ℃ and 60% humidity, place 72 hours, therefore form size 10mm * 150mm and average film thickness is the banded film of 50 μ m to allow solvent evaporation.
Elongate tip with an end of film spurs in the direction that is being parallel to glass baseplate under 300mm/ minute the speed then, and becoming with glass baseplate under 180 ° the angle to spur, measures stripping strength (g/cm).Measuring result sees Table 3 and table 4, in the row that is labeled as " bond strength ".
[in the constant Al electrode corrosion test that applies under the voltage]
The preparation line width is 10 μ m, being spaced apart 10 μ m and being of a size of the Al comb poles of 10mm * 5mm between the line.To be applied to the surface of electrode based on the resin combination of Polyimidesiloxane, and place 72 hours under 23 ℃ and 60% humidity then, be that the paint film of 50 μ m has applied electrode with mean thickness therefore.
The Al comb poles that obtains is being comprised 60 ℃ of temperature, continuously tested under the condition of relative humidity 90% and the constant 7.5V that exerts pressure.For the Al electrode (unit: hour) takes place the used time of corrosion by examining under a microscope measurement.Continuity test carried out maximum 168 hours.The results are shown in Table 3 and table 4, in the row that is labeled as " electrode corrosion test ".In table, the corrosive situation wherein even carrying out continuity test does not take place after 168 hours in clauses and subclauses "＞168 " expressions.
[table 3]
[table 4]
[Comparative Examples 1]
Except that not using reactivity to contain the double imide compound of silyl, adopt the mode identical to prepare based on the resin combination of Polyimidesiloxane with embodiment 1, the evaluation of film forming and film properties then also employing and embodiment 1 identical mode carry out.The character and the evaluation result of composition see Table 5.In the electrode corrosion test, the Al electrode causes circuit to disconnect less than internal corrosion in 168 hours.
[Comparative Examples 2-5]
Except that not using reactivity to contain the double imide compound of silyl, use the organoalkoxysilane hydrolysis-condensation product (name of product: KBM-803P that contains sulfydryl with combination shown in the table 5 and quantity (mass parts), the Shin-Etsu Chemical Co. of manufacturers, Ltd.) or the organoalkoxysilane of hydrogeneous silyl (name of product: 03MS, the Shin-Etsu ChemicalCo. of manufacturers, Ltd.) and titanium isopropylate, adopt the mode identical to prepare based on the resin combination of Polyimidesiloxane with embodiment 1, the evaluation of film forming and film properties then also employing and embodiment 1 identical mode carry out.The results are shown in Table 5.In the electrode corrosion test, the Al electrode less than internal corrosion in 168 hours, causes circuit to disconnect under each situation.
[table 5]
Claims (8)
1. based on the resin combination of Polyimidesiloxane, comprising:
(a) be selected from following polymkeric substance: polyamic acid, it is the tetracarboxylic compound that is selected from aromatic acid's compound and alicyclic tetracarboxylic compound, with the reaction product of aromatic diamine and diamino siloxanes; Polyimidesiloxane with the not busy ring derivatives of the described polyamic acid of expression;
(b) solvent, described solvent be selected from following at least a: straight chain and cyclic amide based solvent; Ester; Ether; Ketone; Alcohol; The urea groups solvent; The sulfoxide group solvent; The sulfuryl solvent; The alkyl solvent; With the halogen radical solvent; With
(c) reactivity of being represented by the structural formula (1) of following demonstration contains the double imide compound of silyl:
Wherein, X represents quadrivalent organic radical group, R
1And R
2The identical or different not replacement of 1-10 carbon atom of expression or replacement univalence hydrocarbyl and m represent integer 1-20,
Wherein said X represents to be selected from quadrivalent organic radical group shown below:
2. according to the composition of claim 1, wherein in the described polymkeric substance of described component (a), based on the quantity of the structure of described diamino siloxanes, with respect to all repeating units of the described polymkeric substance that constitutes described component (a) in conjunction with total amount, be 1-60mol%.
3. according to the composition of claim 1, the described solvent of wherein said component (b) be selected from following at least a: N-Methyl pyrrolidone; Lactone; Carbonic ether; And cyclic ether.
4. according to the composition of claim 1, the quantity of wherein said component (b) is 50-1,900 mass parts, and the quantity of described component (c) is the 5-200 mass parts, the described components of per 100 mass parts (a).
5. the electrode protection material comprises the resin combination based on Polyimidesiloxane according to claim 1.
6. adopt method, comprise the steps: based on the cured product guard electrode of the resin combination of Polyimidesiloxane according to claim 1
Apply described composition to described electrode and
Solidify described composition on the top of described electrode, to form described cured product.
7. film comprises the cured product based on the resin combination of Polyimidesiloxane according to claim 1.
8. comprise production method, comprise the steps: based on the film of the cured product of the resin combination of Polyimidesiloxane according to claim 1
Apply described composition to base material and
Solidify described composition on the top of described base material, to form described cured product.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006157081A JP4772593B2 (en) | 2006-06-06 | 2006-06-06 | Polyimide silicone resin composition |
| JP2006157081 | 2006-06-06 | ||
| JP2006-157081 | 2006-06-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101085868A CN101085868A (en) | 2007-12-12 |
| CN101085868B true CN101085868B (en) | 2011-05-18 |
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| KR (1) | KR101297940B1 (en) |
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| JP5304106B2 (en) * | 2008-08-28 | 2013-10-02 | 三菱化学株式会社 | Bisimide phenol compound and method for producing the same |
| KR101566768B1 (en) * | 2008-11-10 | 2015-11-06 | 아지노모토 가부시키가이샤 | Resin composition for printed wiring board |
| JP5206977B2 (en) * | 2009-03-12 | 2013-06-12 | 信越化学工業株式会社 | Novel polyimide silicone, photosensitive resin composition containing the same, and pattern forming method |
| JP5499312B2 (en) * | 2009-09-30 | 2014-05-21 | 信越化学工業株式会社 | NOVEL POLYIMIDE SILICON HAVING ALCOHOLIC HYDROXY AND PROCESS FOR PRODUCING THE SAME |
| KR101757023B1 (en) * | 2011-06-14 | 2017-07-11 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Cross-linked polyimide resin and method for producing same, adhesive resin composition and cured product thereof, cover lay film, circuit board, heat-conductive substrate, and heat-conductive polyimide film |
| CN114032060B (en) * | 2021-11-26 | 2023-05-02 | 广东粤港澳大湾区黄埔材料研究院 | Polyimide composition, polyimide compound, preparation and application thereof |
| CN114181393B (en) * | 2022-01-27 | 2023-06-02 | 中国科学院过程工程研究所 | Semi-alicyclic polyimide material, semi-alicyclic polyimide film, and preparation methods and applications thereof |
| CN115466393B (en) * | 2022-10-19 | 2023-08-08 | 开封大学 | Incombustible light composite material and preparation method thereof |
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| JPH0826153B2 (en) * | 1987-11-12 | 1996-03-13 | チッソ株式会社 | Soluble imide group-containing silicon-based oligomer and method for producing the same |
| JP2631878B2 (en) | 1988-09-27 | 1997-07-16 | 宇部興産株式会社 | Polyimide siloxane composition and film |
| JP2513096B2 (en) * | 1991-08-15 | 1996-07-03 | 信越化学工業株式会社 | Curable compound, method for producing the same, insulating protective film forming agent, and protective agent for electronic parts |
| JP3395269B2 (en) * | 1993-07-16 | 2003-04-07 | チッソ株式会社 | Polyimide siloxane film with low thermal conductivity |
| JP2003213129A (en) | 2002-01-29 | 2003-07-30 | Shin Etsu Chem Co Ltd | Polyimide silicone resin composition |
| JP4019254B2 (en) * | 2002-04-24 | 2007-12-12 | 信越化学工業株式会社 | Conductive resin composition |
| JP4041771B2 (en) | 2003-05-22 | 2008-01-30 | 信越化学工業株式会社 | Polyimide silicone resin composition |
| JP2006117710A (en) * | 2004-10-19 | 2006-05-11 | Shin Etsu Chem Co Ltd | Polyimide silicone resin composition |
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| CN101085868A (en) | 2007-12-12 |
| KR20070116727A (en) | 2007-12-11 |
| JP4772593B2 (en) | 2011-09-14 |
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