CN102449070B - Resin composition, cured product, and circuit board using same - Google Patents

Resin composition, cured product, and circuit board using same Download PDF

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Publication number
CN102449070B
CN102449070B CN201080024194.9A CN201080024194A CN102449070B CN 102449070 B CN102449070 B CN 102449070B CN 201080024194 A CN201080024194 A CN 201080024194A CN 102449070 B CN102449070 B CN 102449070B
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polyimide precursor
resin combination
resin
general formula
diamines
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CN102449070A (en
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孙恩海
足立弘明
佐佐木洋朗
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Asahi Kasei Corp
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Asahi Chemical Co Ltd
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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
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • 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
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

Abstract

Disclosed is a resin composition which is suppressed in warping and rebound properties after thermosetting, and provides a cured film having excellent chemical resistance, heat resistance and flame retardancy. Specifically disclosed is a resin composition containing a polyimide precursor that has a polyether structure and a compound that has a thermally crosslinkable functional group, said resin composition being characterized in that the polyimide precursor has an imidization ratio of 40-98% (inclusive).

Description

The circuit substrate of resin combination, cured article and this cured article of use
Technical field
The present invention relates to its circuit substrate of surface protection film as semiconductor element, interlayer dielectric, bonding sheet, use in printed circuit board protection insulating film useful stable on heating resin combination, cured article and use.
Background technology
Surface protection film, interlayer dielectric, use in printed circuit board protection insulating film as semiconductor element, used the resin combination that contains polyimide gradually due to excellent heat resistance.Particularly, when being applied to flexible wired circuit, require the warpage after resin combination solidifies few.The resin combination of the warpage as excellent heat resistance and after having prevented from solidifying, has the document to disclose the resin combination (for example,, referring to patent documentation 1) that a kind of polyimide consisting of ester end oligopolymer and amine end oligopolymer is ink.But, for such resin combination, in order to carry out imidization, at least need to heat-treat above at 250 ℃, the contraction of formed polyimide resin is large, processibility existing problems.In addition, while using Copper Foil in circuit material, carboxyl and wiring material react, and have the problem of the oxidation that wiring material occurs.
On the other hand, in order to be cured at low temperatures, and the warpage after suppress solidifying, there is document to disclose and use diamino siloxanes as the Polyimidesiloxane precursor (for example,, referring to patent documentation 2, patent documentation 3) of two amine components.But, these Polyimidesiloxane precursors are being coated on circuit substrate, and are being made its imidization and while forming the protection overlay film of circuit, after pre-preg and bonding operation in there is the bonding hypodynamic problem between protection overlay film and adhesive sheet.
In addition, there is document to disclose to use alkyl oxide diamines, in photosensitive dry film resist purposes, reduce imidization temperature and the polyimide precursor (for example,, referring to patent documentation 4) of the non-silicone-based of part imidization.But the flexibility of the cured article consisting of the polyimide precursor of these part imidizations is insufficient.
In addition, when the surface mounting assembly to circuit substrate, during the circuit protection film that is formed for preventing that scolding tin from adhering to etc., share sometimes covering layer film and photosensitivity anticorrosive additive material beyond needing the position of scolding tin.In this case, need lamination processing, exposure process, developing procedure etc., so manufacturing process is complicated.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 2-145664 communique
Patent documentation 2: Japanese kokai publication sho 57-143328 communique
Patent documentation 3: Japanese kokai publication sho 58-13631 communique
Patent documentation 4: TOHKEMY 2006-321924 communique
Summary of the invention
The present invention carries out in view of the above problems, and its object is to provide a kind of resin combination, and it has suppressed warpage and the rebound resilience after thermofixation, can form the cured film of chemical proofing, thermotolerance, excellent in flame retardance.
The inventor conducts in-depth research in order to solve above-mentioned problem, found that, the polyimide precursor that comprises the imide rate that has specific structure and have specified range and the resin combination with the compound of heat cross-linking functional group can compatibly solve this problem, based on this opinion, have completed the present invention.That is, the present invention is as described below.
Resin combination of the present invention is to contain the resin combination that has the polyimide precursor of polyether structure and have the compound of heat cross-linking functional group, it is characterized in that, the imide rate of described polyimide precursor is more than 40% below 98%.
In resin combination of the present invention, the imide rate of preferred described polyimide precursor is more than 40% below 95%.
In resin combination of the present invention, the polyimide portion that preferred described polyimide precursor comprises the structure with following general formula (1).
Figure BDA0000115023190000021
(in formula (1), Z 1and Z 2represent 4 valency organic groups; R 1, R 2, R 3, R 4and R 5represent the alkylidene group that carbonatoms is 1～5, and can there is side chain.M, n and q represent 1～50 integer.)
In resin combination of the present invention, preferably in the whole diamines in described polyimide precursor, the content of diamines with the structure of following general formula (2) be 15 % by mole above below 85 % by mole.
Figure BDA0000115023190000022
(in formula (2), R 1, R 2, R 3, R 4and R 5represent the alkylidene group that carbonatoms is 1～5, and can there is side chain.M, n and q represent 1～50 integer.)
In resin combination of the present invention, preferably in the diamines of the described structure with general formula (2), R 2, R 3, R 4and R 5the alkylidene group representing is two or more alkylidene group.
In resin combination of the present invention, there is the weight-average molecular weight of diamines of structure of general formula (2) described in preferably in 400 to 2000 scope.
In resin combination of the present invention, there is the weight-average molecular weight of diamines of structure of general formula (2) described in preferably in 600 to 2000 scope.
In resin combination of the present invention, preferred described polyimide precursor comprises the polyamic acid portion with polyamic acid structure and the polyimide portion with polyimide structures, compare with described polyamic acid portion, in described polyimide portion, contain the diamines described in more with the structure of general formula (2).
In resin combination of the present invention, the Z of preferred described general formula (1) 1and Z 2the 4 valency organic groups for following general formula (3) expression.
(in formula (3), R 17expression-O-,-SO 2-or-CO-.)
In resin combination of the present invention, the imide rate of preferred described polyimide precursor is more than 50%, and imide rate D% and 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride meets the relational expression of (E >=0.6D-30) with respect to the relation between content E % by mole of all acid composition.
In resin combination of the present invention, the Z of preferred described general formula (1) 1and Z 2by from 3,3 ', 4, in 4 '-sulfobenzide tetracarboxylic dianhydride, remove 4 valency organic group residues after dicarboxylic anhydride structure and from 3,3 ', 4, the 4 valency organic group residues of removing in 4 '-benzophenone tetracarboxylic dianhydride after dicarboxylic anhydride structure form.
In resin combination of the present invention, the Z of preferred described general formula (1) 1and Z 2by from 3,3 ', 4, in 4 '-sulfobenzide tetracarboxylic dianhydride, remove 4 valency organic group residues after dicarboxylic anhydride structure and from 4, the 4 valency organic group residues of removing after dicarboxylic anhydride structure in the two Tetra hydro Phthalic anhydrides of 4 '-oxygen form.
In resin combination of the present invention, the polyimide portion that comprises the structure with following general formula (4) in preferred described polyimide precursor.
Figure BDA0000115023190000041
(in formula (4), Z 3and Z 4represent 4 valency organic groups, R 18represent the alkyl that carbonatoms is 2～10, h represents 1～50 integer.)
In resin combination of the present invention, preferably in the whole diamines in described polyimide precursor, the content of diamines with the structure of following general formula (5) be 15 % by mole above below 85 % by mole.
Figure BDA0000115023190000042
(in formula (5), R 18represent the alkyl that carbonatoms is 2～10, h represents 1～50 integer.)
In resin combination of the present invention, preferably in the diamines in described polyimide precursor, also comprise the aromatic diamine that at least one following general formula (6) represents.
Figure BDA0000115023190000043
(in formula (6), R 19with following formula (7) or following general formula (8), represent.)
Figure BDA0000115023190000044
(in formula (8), R 20represent singly-bound ,-O-,-SO 2-or-C (CH 3) 2-.)
In resin combination of the present invention, preferred described aromatic diamine is two (3-amino-benzene oxygen) benzene of 1,3-.
In resin combination of the present invention, there is the resin that the compound of heat cross-linking functional group forms with monomer polymerization described in preferably and there is flame retardant resistance.
In resin combination of the present invention, the compound described in preferably with heat cross-linking functional group is at least one compound selecting in the group that free triazine based compound, benzoxazine based compound, epoxy based compound and blocked isocyanate based compound form.
In resin combination of the present invention, the compound described in preferably with heat cross-linking functional group is to have the compound that does not need in fact the heat cross-linking of heat cross-linking promotor functional group.
In resin combination of the present invention, preferably with respect to polyimide precursor described in 100 mass parts contain 1 mass parts～40 mass parts described in there is the compound of heat cross-linking functional group.
In resin combination of the present invention, the imide rate of preferred described polyimide precursor is more than 40% below 90%.
In resin combination of the present invention, the acid number of preferred described polyimide precursor is more than 16mgKOH/g.
In resin combination of the present invention, preferably described resin combination was preserved after 3 months to being changed to below 20% of viscosity.
In resin combination of the present invention, the acid number of preferred described polyimide precursor is that 16mgKOH/g is above to 70mgKOH/g, described resin combination is preserved after 1 month to being changed to below 10% of viscosity.
In resin combination of the present invention, the end of the main polymer chain of preferred described polyimide precursor has carried out end-blocking with at least one derivative (end-capping reagent) in the group of selecting free monoamine derivative or carboxylic acid derivative to form.
In resin combination of the present invention, preferably the Young's modulus after thermofixation is 0.3～1.4GPa, and in solder bath, when flooding 60 seconds for 260 ℃, nothing expands, burns.
In resin combination of the present invention, preferably also contain fire retardant, in described resin combination, halogen series elements content is below 1000ppm, has the flame retardant resistance of VTM-0 according to UL-94 standard.
Resin composition for screen printing of the present invention is above-mentioned resin combination, it is characterized in that, its solid component concentration is more than 45%; By silk screen printing, on base material, print, dry after, dry film thickness is more than 15 μ m, and spreads and sinks in that to ooze be below 40 μ m.
The protective membrane of tellite of the present invention forms and is characterised in that with material, and it consists of above-mentioned resin combination.
Cured article of the present invention is characterised in that, it is by obtaining above-mentioned resin combination thermofixation.
Circuit substrate of the present invention is characterised in that, it possesses: the surperficial above-mentioned cured article with base material described in the base material of wiring and coating.
Printed circuit board (PCB) of the present invention is characterised in that, it obtains by comprising the method for following operation: use above-mentioned resin composition for screen printing, and have on the flexible printed circuit board of parts installation portion, this resin combination is printed at the position that utilizes silk screen print method to install beyond needed bonding part at parts.
Polyimide precursor of the present invention contains tetracarboxylic dianhydride and the diamines with alkylether radicals of following general formula (2) expression and the polymkeric substance of at least one aromatic diamine that following general formula (6) represents that following general formula (9) represents, it is characterized in that, the imide rate of polyimide precursor is more than 40% below 98%.
Figure BDA0000115023190000061
(in formula (9), R 21expression-SO 2-.)
(in formula (2), R 1, R 2, R 3, R 4and R 5represent the alkylidene group that carbonatoms is 1～5, and can there is side chain.M, n and q represent 1～50 integer.)
Figure BDA0000115023190000063
(in formula (6), R 19with following formula (7) or following general formula (8), represent.)
Figure BDA0000115023190000064
(in formula (8), R 20represent singly-bound ,-O-,-SO 2-or-C (CH 3) 2-.)
In polyimide precursor of the present invention, in preferred described tetracarboxylic dianhydride, also contain 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride.
In polyimide precursor of the present invention, preferably imide rate is more than 50%, and imide rate D% and 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride meets the relational expression of (E >=0.6D-30) with respect to the relation between content E % by mole of all acid composition.
In polyimide precursor of the present invention, preferably in the diamines of structure with described general formula (2), R 2, R 3, R 4and R 5the alkylidene group representing is two or more alkylidene group.
In polyimide precursor of the present invention, preferably there is the weight-average molecular weight of diamines of structure of described general formula (2) in 400 to 2000 scope.
In polyimide precursor of the present invention, preferably there is the weight-average molecular weight of diamines of structure of described general formula (2) in 600 to 2000 scope.
In polyimide precursor of the present invention, preferably it comprises the polyamic acid portion with polyamic acid structure and the polyimide portion with polyimide structures, compare the diamines that contains the structure more with described general formula (2) in described polyimide portion with described polyamic acid portion.
According to the present invention, a kind of resin combination can be provided, it has suppressed warpage and the rebound resilience after thermofixation, can form the cured film of chemical proofing, thermotolerance, excellent in flame retardance.
Embodiment
Below, the present invention is specifically described.
Resin combination of the present invention is to comprise the resin combination that has the polyimide precursor of polyether structure and have the compound of heat cross-linking functional group, and the imide rate of polyimide precursor is more than 40% below 98%.
Resin combination of the present invention is by comprising the polyimide precursor with polyether structure, thereby can control second-order transition temperature and the Young's modulus of thermofixation after fixing thing, and warpage is few, can show low-resilience.And resin combination of the present invention forms compound crosslinked with heat cross-linking functional group after thermofixation.In resin combination of the present invention, owing to forming chemically crosslinked thering is the polyimide precursor of polyether structure and have between the compound of heat cross-linking functional group, simultaneously, the polyimide precursor with polyether structure has polyoxy alkylidene chain, therefore by interaction local between macromolecular chain, form three-dimensional network, thereby can show thermotolerance.In addition, if the imide rate of polyimide precursor is below 98%, fully residual with the carboxyl having in the polyimide precursor of compound crosslink of heat cross-linking functional group, after solidifying, given play to chemical proofing, thermotolerance.In addition, if the imide rate of polyimide precursor is more than 40%, the carboxyl residue that dissolves in alkaline solution after solidifying reduces, and can give play to chemical proofing, thermotolerance.Herein, the imide rate of polyimide precursor is preferably below 95%, more preferably below 90%.It should be noted that, the method for recording in the item of this imide rate by following embodiment (mensuration of imide rate) is measured.
(A) polyimide precursor
As long as having polyether structure, polyimide precursor is not particularly limited.In addition, preferably use the polyimide precursor of the polyimide portion that comprises the structure with following general formula (1).
(in formula (1), Z 1and Z 2represent 4 valency organic groups; R 1, R 2, R 3, R 4and R 5represent the alkylidene group that carbonatoms is 1～5, and can there is side chain.M, n and q represent 1～50 integer.)
In addition, in the whole diamines in polyimide precursor, the content of diamines with the structure of following general formula (2) be preferably 15 % by mole above below 85 % by mole.
Figure BDA0000115023190000082
(in formula (2), R 1, R 2, R 3, R 4and R 5represent the alkylidene group that carbonatoms is 1～5, and can there is side chain.M, n and q represent 1～50 integer.)
In above-mentioned general formula (2), from the aspect of the adaptation with substrate, R 2, R 3, R 4and R 5in preferably include two or more alkylidene groups.
The concrete example of the diamines representing as above-mentioned general formula (2), can enumerate polyethyleneoxide diamine, polypropyleneoxide diamine, other polyoxy alkylidene diamines that comprise the different oxyalkylene of carbochain number etc.As polyoxy alkylidene Diamines, can enumerate the material etc. that the polypropyleneoxide diamine such as polyethyleneoxide diamine, JEFFAMINE D-230, D-400, D-2000, D-4000, JEFFAMINE XTJ-542, XTJ-533, the XTJ-536 etc. such as JEFFAMINE ED-600, ED-900 that U.S. Huntsman company manufactures, ED-2003, EDR-148, HK-511 have polytetramethylene ethylidene.Wherein, the EDR-148 that molecular weight ratio is lower, D-230, D-400, HK-511 etc. can form the polymkeric substance with higher second-order transition temperature, therefore in the purposes that needs thermotolerance, chemical proofing, preferably use.The excellences such as the flexibility of the D-2000 that on the other hand, molecular weight ratio is higher etc., low boiling point solvent solvability.These diamines can be separately or two or more mix and use.
In addition, from the aspect of the balance of thermotolerance, chemical proofing and flexibility, solvent soluble, the weight-average molecular weight of polyoxy alkylidene diamines is preferably 400～2000, is particularly preferably 600～2000.Polyoxy alkylidene diamines as having such weight-average molecular weight, is preferably used ED-600, ED-900, XTJ-542.Wherein, the polyoxy alkylidene diamines that comprises the different oxyalkylene of carbochain number (for example has polyethyleneoxide diamine ED-600, the ED-900 of ethylidene and propylidene and has propylidene and 1, the polyethyleneoxide diamine XTJ-542 of 4-butylidene, XTJ-533) because solvent soluble further improves, thereby particularly preferably use.
In addition, when the diamines that above-mentioned general formula (2) represents is used the higher material of purity, as polyamic acid and polyimide, easily obtain the material of high molecular.The purity of the diamines that above-mentioned general formula (2) represents is preferably more than 95%, more preferably more than 97%, more preferably more than 98.5%.
The content of the diamines that above-mentioned general formula (2) represents is preferably 15 % by mole～85 % by mole with respect to whole diamines.More preferably 25 % by mole～60 % by mole, more preferably 30 % by mole～50 % by mole.If more than 15 % by mole, demonstrate low warpage, low-resilience, if below 85 % by mole, solvent resistance and excellent heat resistance.
As operable other diamines outside the diamines representing at above-mentioned general formula (2), for example, can enumerate 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 3,3 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether, two (3-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (3-(3-amino-benzene oxygen) phenyl) ether, two (4-(4-amino-benzene oxygen) phenyl) ether, two (3-(3-amino-benzene oxygen) phenoxy group) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-(4-amino-benzene oxygen) phenoxy group) benzene, two (3-(3-(3-amino-benzene oxygen) phenoxy group) phenyl) ether, two (4-(4-(4-amino-benzene oxygen) phenoxy group) phenyl) ether, two (3-(3-(3-amino-benzene oxygen) phenoxy group) phenoxy group) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-(4-(4-amino-benzene oxygen) phenoxy group) phenoxy group) benzene, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, two [4-(3-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl]-1,1,1,3,3 of 2,2-, 3-HFC-236fa, two [4-(4-amino-benzene oxygen) phenyl]-1,1,1,3,3 of 2,2-, 3-HFC-236fa, O-Phenylene Diamine, mphenylenediamine, Ursol D, two (3-aminophenyl) thioether, two (4-aminophenyl) thioether, two (3-aminophenyl) sulfoxide, two (4-aminophenyl) sulfoxide, two (3-aminophenyl) sulfone, two (4-aminophenyl) sulfone, two [4-(3-amino-benzene oxygen) phenyl] butane of 2,2-, α, ω-bis-(2-amino-ethyl) polydimethylsiloxane, α, ω-bis-(3-aminopropyl) polydimethylsiloxane, α, ω-bis-(4-aminobutyl) polydimethylsiloxane, α, ω-bis-(4-aminophenyl) polydimethylsiloxane, α, ω-bis-(3-aminopropyl) polydiphenylsiloxane etc., but be not limited to these.Be preferably 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, 1, two (3-(3-amino-benzene oxygen) phenoxy group) benzene, 1 of 3-, two (3-amino-benzene oxygen) benzene of 3-.
As polyimide precursor, can use and comprise the material that mainly there is the polyamic acid portion of polyamic acid structure in molecular chain and mainly there is the polyimide portion of polyimide structures.In this situation, preferably use and compare the polyimide precursor of the diamines that contains the structure more with above-mentioned general formula (2) in polyimide portion with polyamic acid portion.By the diamines that contains the structure more with above-mentioned general formula (2) in polyimide portion, the stable excellence of polyimide precursor.
From the aspect of solvent soluble, the Z of above-mentioned general formula (1) 1and Z 2be preferably the 4 valency organic groups that following general formula (3) represents.
Figure BDA0000115023190000101
(in formula (3), R 17expression-O-,-SO 2-or-CO-.)
The 4 valency organic groups that represent as above-mentioned general formula (3), can enumerate the 4 valency organic group residues removed from tetracarboxylic dianhydride after dicarboxylic anhydride structure etc.As 4 such valency organic group residues, specifically, can enumerate from 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 3, the two Tetra hydro Phthalic anhydrides, 4 of 3 '-oxygen, remove 4 valency organic group residues after dicarboxylic anhydride structure etc. in the two Tetra hydro Phthalic anhydrides of 4 '-oxygen.
Wherein, as the Z of above-mentioned general formula (1) 1and Z 2, from the aspect of solvent soluble, be preferably from 3,3 ', 4, in 4 '-sulfobenzide tetracarboxylic dianhydride, remove 4 valency organic group residues after dicarboxylic anhydride structure.In addition, from obtain solvent soluble and with the aspect of the balance of the adaptation of substrate, be preferably from 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride and 3,3 ', 4, in the mixture of 4 '-benzophenone tetracarboxylic dianhydride, remove 4 valency organic group residues after dicarboxylic anhydride structure or from 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride and 4, removes 4 valency organic group residues after dicarboxylic anhydride structure in the mixture of the two Tetra hydro Phthalic anhydrides of 4 '-oxygen.
In addition, in not damaging the scope of effect of the present invention, can use existing known tetracarboxylic dianhydride.As such tetracarboxylic dianhydride, can exemplify aromatic tetracarboxylic acid's dianhydride, aliphatics tetracarboxylic dianhydride.As aromatic tetracarboxylic acid's dianhydride, can enumerate pyromellitic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2,2-, two (2,3-dicarboxyl phenyl) the propane dianhydrides of 2,2-, two (3,4-dicarboxyl phenyl) the ethane dianhydrides of 1,1-, two (2,3-dicarboxyl phenyl) the ethane dianhydrides of 1,1-, two (3,4-dicarboxyl phenyl) methane dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride, 1,3-dihydro-1,3-dioxo-5-isobenzofuran carboxylic acid-Isosorbide-5-Nitrae-phenylene ester, 4-(2,5-dioxo tetrahydrofuran (THF)-3-yl)-1,2,3,4-naphthane-1,2-dicarboxylic acid anhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2,2-, two (4-(3, the 4-di carboxyl phenyloxy) phenyl) hexafluoropropane dianhydrides of 2,2-, two (4-(3, the 4-dicarboxyl benzoyl oxygen base) phenyl) hexafluoropropane dianhydrides of 2,2-, 2,2 '-bis-(trifluoromethyl)-4,4 '-bis-(3,4-di carboxyl phenyloxy) biphenyl acid acid anhydride etc.
As aliphatics tetracarboxylic dianhydride, can enumerate tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic acid dianhydride, dicyclo [2,2,2] be pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride.
In polyimide precursor of the present invention, from the aspect of storage stability, imide rate is preferably more than 50%.By making imide rate D, be more than 50%, the concentration of polyamic acid reduces, so storage stability improves.In addition, imide rate D% and 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride preferably meets the relational expression of (E >=0.6D-30) with respect to the relation of the content Emol% of all acid composition.In above-mentioned relation formula, in the situation that imide rate increases, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride is with respect to the content E % by mole increase of all acid composition, can make up thus the reduction of the solubility that the increase of imide rate causes, even if also can keep solvent soluble at low temperatures, thereby more preferably.
The polyimide precursor with polyether structure more preferably comprises the polyimide portion of the structure with following general formula (4).
Figure BDA0000115023190000111
(in formula (4), Z 3and Z 4represent 4 valency organic groups, R 18represent the alkyl that carbonatoms is 2～10, h represents 1～50 integer.)
In order to obtain comprising the polyimide precursor of the polyimide portion of the above-mentioned structure with general formula (4), the compound that preferably uses following general formula (5) to represent.
Figure BDA0000115023190000112
(in formula (5), R 18represent the alkyl that carbonatoms is 2～10, h represents 1～50 integer.)
The concrete example of the diamines representing as above-mentioned general formula (5), can enumerate such as polytetramethylene ether-bis--cinnamyl o-aminobenzoate, polytetramethylene ether-bis--gavaculine ester, polytetramethylene ether-bis--para-amino benzoic acid ester, polytrimethylene ether-bis--cinnamyl o-aminobenzoate, polytrimethylene ether-bis--gavaculine ester, polytrimethylene ether-bis--para-amino benzoic acid ester etc., but be not limited to these.Wherein, preferably two ends are the material of para-amino benzoic acid ester group, wherein, preferably use polytetramethylene ether-bis--para-amino benzoic acid ester.In addition, also can use diamines of more than two kinds.
The diamines that above-mentioned general formula (5) represents with respect to whole diamines be preferably 15 % by mole above below 85 % by mole, more preferably 25～60 % by mole, more preferably 25～50 % by mole, most preferably be 30～50 % by mole.If more than 15 % by mole, can demonstrate low warpage, low-resilience, if below 85 % by mole, solvent resistance and excellent heat resistance.
Due to thermotolerance and solvability excellence, thereby in the diamines in polyimide precursor of the present invention, preferably also comprise the aromatic diamine that at least one following general formula (6) represents.It is believed that this is to have because of aromatic diamine the effect that aromatic nucleus produces.
Figure BDA0000115023190000121
(in formula (6), R 19with following formula (7) or following general formula (8), represent.)
(in formula (8), R 20represent singly-bound ,-O-,-SO 2-or-C (CH 3) 2-.)
The concrete example of the diamines representing as above-mentioned general formula (6), can enumerate 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4, 4 '-bis-(3-amino-benzene oxygen) biphenyl, 4, 4 '-bis-(4-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] ether, two [4-(3-amino-benzene oxygen) phenyl] ether, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] the trifluoro propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] the trifluoro propane of 2-.Wherein, from stable on heating aspect, particularly preferably 1, two (3-amino-benzene oxygen) benzene of 3-.
The content of the diamines that above-mentioned general formula (6) represents is preferably 15 % by mole～85 % by mole with respect to whole diamines.More preferably 40 % by mole～75 % by mole, more preferably 50 % by mole～70 % by mole.If more than 15 % by mole, solvent resistance is excellent, if below 85 % by mole, can suppress warpage and rebound resilience.
In polyimide precursor of the present invention, the aspect of the cross-linking density from solidifying, more than acid number is preferably 16mgKOH/g.If acid number is more than 16mgKOH/g, after thermofixation and have while carrying out chemically crosslinked between the compound of heat cross-linking functional group, can access sufficient cross-linking density, chemical proofing is excellent.
In polyimide precursor of the present invention, from the aspect of storage stability, acid number is preferably below 70mgKOH/g.If acid number is below 70mgKOH/g, easily obtain the balance of storage stability and solvent soluble.Acid number is more preferably in the scope below 50mgKOH/g, further preferably in the scope below 40mgKOH/g.
Below the manufacture method of polyimide precursor is described.The manufacture method of polyimide precursor of the present invention can be applied all methods of the polyimide precursor manufactured that comprises known method.Wherein, preferably in organic solvent, react.As the solvent using in such reaction, for example, can enumerate N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, gamma-butyrolactone, 1,2-glycol dimethyl ether, tetrahydrofuran (THF), 1,3-dioxane, Isosorbide-5-Nitrae-dioxane, dimethyl sulfoxide (DMSO), benzene,toluene,xylene, trimethylbenzene, phenol, cresols, methyl benzoate, ethyl benzoate, butyl benzoate etc.They can separately or mix two or more use.The concentration of the reaction raw materials in this reaction is generally 2 quality %～60 quality %, is preferably 30 quality %～50 quality %.
For the mol ratio of the dicarboxylic anhydride that reacts and diamines in 0.8～1.2 scope.In the time of within the scope of this, can improve molecular weight, elongation etc. are also excellent.Be preferably 0.9～1.1, more preferably 0.95～1.05.
The weight-average molecular weight of polyimide precursor is preferably more than 5000 below 100000.Herein, weight-average molecular weight refers to and usings the polystyrene of known number average molecular weight as standard, by the molecular weight of gel permeation chromatography.Weight-average molecular weight is more preferably more than 10000 below 60000, most preferably is more than 20000 below 50000.If weight-average molecular weight is more than 5000 below 100000, use the warpage of the protective membrane that resin combination obtains to improve, low-resilience and excellent heat resistance.In addition, during coating and printing, can print with desired thickness and do not spread and sink in and ooze, and the mechanical properties such as the elongation of resulting protective membrane is excellent.
Polyimide precursor obtains by the following method.First, make reaction raw materials at room temperature carry out polycondensation, thereby produce polyimide precursor.Now, equivalents is made as acid anhydrides > diamine compound.Next, this polyimide precursor heating (preferably 100 ℃～400 ℃) is carried out to imidization, or use the imide agents such as diacetyl oxide to carry out chemical imidization, thereby obtain having the acid anhydrides end polyimide of the repeat unit structure corresponding with polyamic acid.By heating, undertaken in the situation of imidization, in order to remove the water as by product, also preferably make entrainer (being preferably toluene, dimethylbenzene) coexist, utilize Dean-Stark type dewatering unit to dewater under refluxing.And then, preferably in the temperature below 100 ℃, more preferably add diamine compound composition at the temperature below 60 ℃, make its polyaddition reaction 0.5 hour～12 hours, thereby can synthesize polyimide precursor of the present invention.
In addition, the end of the main polymer chain of polyimide precursor preferably uses the end-capping reagent consisting of monoamine derivative or carboxylic acid derivative to carry out end-blocking.By sealing the end of the main polymer chain of polyimide, storage stability is excellent.
As the end-capping reagent being formed by monoamine derivative, for example, can enumerate aniline, Ortho Toluidine, meta-aminotoluene, para-totuidine, 23 dimethyl aniline, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, Ortho-Chloro aniline, m-chloro aniline, p-Chlorobenzoic acid amide, o-bromoaniline, m-bromoaniline, para-bromoaniline, o-Nitraniline, m-nitraniline, p-Nitroaniline, Ortho-Aminophenol, Metha Amino Phenon, p-aminophenol, o-anisidine, m-anisidine, P-anisidine, O-ethoxyl amine, m-oxethyl aniline, p-ethoxyaniline, o-Aminobenzaldehyde, NSC 36957, p-Aminobenzaldehyde, adjacent aminobenzonitrile, between aminobenzonitrile, to aminobenzonitrile, 2-phenylaniline, 3-phenylaniline, 4-phenylaniline, 2-aminophenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-diaminodiphenyl sulfide, 3-diaminodiphenyl sulfide, 4-diaminodiphenyl sulfide, 2-ADP sulfone, 3-ADP sulfone, 4-ADP sulfone, alpha-naphthylamine, beta-naphthylamine, 1-amino-beta naphthal, 5-amino-1-naphthols, 2-amino-1-naphthols, 4-amino-1-naphthols, 5-amino-beta naphthal, 7-amino-beta naphthal, 8-amino-1-naphthols, 8-amino-beta naphthal, 1-amino anthracene, 2-amino anthracene, the aromatic series monoamines such as 9-amino anthracene, are wherein preferably used the derivative of aniline.They may be used alone, can also be two or more kinds in combination.
As the end-capping reagent being formed by carboxylic acid derivative, mainly can enumerate carboxylic acid anhydride derivative, can enumerate Tetra hydro Phthalic anhydride, maleic anhydride, 2, 3-benzophenone dicarboxylic acid acid anhydride, 3, 4-benzophenone dicarboxylic acid acid anhydride, 2, 3-dicarboxyl phenyl ether acid acid anhydride, 3, 4-dicarboxyl phenyl ether acid acid anhydride, 2, 3-biphenyl dicarboxylic acid acid anhydride, 3, 4-biphenyl dicarboxylic acid acid anhydride, 2, 3-Dicarboxy diphenylsulfone acid anhydrides, 3, 4-Dicarboxy diphenylsulfone acid anhydrides, 2, 3-dicarboxyl diphenyl sulfide acid anhydrides, 3, 4-dicarboxyl diphenyl sulfide acid anhydrides, 1, 2-naphthalic anhydride, 2, 3-naphthalic anhydride, 1, 8-naphthalic anhydride, 1, 2-anthracene dicarboxylic acid anhydride, 2, 3-anthracene dicarboxylic acid anhydride, 1, the aromatic dicarboxylic acid acid anhydrides such as 9-anthracene dicarboxylic acid anhydride.In these aromatic dicarboxylic acid acid anhydrides, preferably use Tetra hydro Phthalic anhydride.They may be used alone, can also be two or more kinds in combination.
Resulting polyimide can not carry out desolventizing and directly make resin combination of the present invention, or makes resin combination of the present invention after further mixing necessary solvent, additive etc.
(B) there is the compound of heat cross-linking functional group
As the compound with heat cross-linking functional group, as long as there is heat cross-linking functional group, be not particularly limited, yet the resin preferably forming with monomer polymerization has flame retardant resistance.If the resin forming with monomer polymerization has flame retardant resistance, contribute to the fire-retardant of resin combination, can easily show the flame retardant resistance of resin combination.In addition, as the compound with heat cross-linking functional group, be preferably at least one compound in the group of selecting free triazine based compound, benzoxazine based compound, epoxy based compound and blocked isocyanate based compound composition.
The compound that triazine based compound, benzoxazine based compound, epoxy based compound and blocked isocyanate based compound etc. have heat cross-linking functional group is by demonstrating elastomeric compound with resin-bonded originally, has by snappiness the easily character of warpage.The inventor be conceived to have low warpage properties polyimide precursor, with the easily combination of the compound with heat cross-linking functional group of warpage by snappiness.In addition, by the imide rate of polyimide precursor is adjusted into 40% to 98%, can realize the object of improving chemical proofing when maintaining the low warpage properties of polyimide precursor.
As triazine based compound, preferably in a part, there is the compound of two above triazine rings, compound, melamine class and melamine cyanurate class etc. that preferably trimeric cyanamide and following general formula (10) or following general formula (11) represent.
(in formula (10), X, Y, Z represent respectively hydrogen atom, Sauerstoffatom, sulphur atom, nitrogen-atoms.R 6～R 11be respectively hydrogen atom or carbonatoms and be the alkoxyalkyl that 1～5 alkyl or carbonatoms are 1～5, when X, Y, Z are hydrogen atom, because hydrogen atom does not have substituting group, therefore on structural formula, do not have R 6～R 11.)
Figure BDA0000115023190000152
(in formula (11), R 12～R 14represent respectively the alkoxyalkyl that alkyl that hydrogen atom, carbonatoms are 1～5 or carbonatoms are 1～5.)
The concrete example of the compound representing as above-mentioned general formula (10), can enumerate hexamethylolmelamine, six hydroxyl melamine-butyls, part methylolation trimeric cyanamide and alkylation body, tetra methylol benzo guanamine, part methylolation benzo guanamine and alkylation body thereof etc.The concrete example of the compound representing as above-mentioned general formula (11), can enumerate isocyanuric acid, trimethylammonium isocyanuric acid ester, triethyl isocyanuric acid ester, three (n-propyl) isocyanuric acid ester, diethyl isocyanuric acid ester, methyl isocyanuric acid ester etc.
As melamine class, can enumerate trimeric cyanamide, melamine derivative, have and the compound of the similar structure of trimeric cyanamide and the condenses of trimeric cyanamide etc.Concrete example as melamine class, for example, can enumerate methylolation trimeric cyanamide, melon, cyanurodiamide, 2,4-diaminostilbene, 3,5-triazine, amidino groups trimeric cyanamide, cyano group trimeric cyanamide, aryl guanamines, melam, melem, trimerization dicyan acetonitrile etc.
As melamine cyanurate class, can enumerate the reaction with same mole product of cyanuric acid and melamine class.In addition, several amino in melamine cyanurate class or hydroxyl can replace with other substituting groups.Wherein, melamine cyanurate can obtain in the following manner: for example, by the aqueous solution of the aqueous solution of cyanuric acid and trimeric cyanamide, 90 ℃～100 ℃ stirrings, make it reaction, by generated sedimentation and filtration, thereby obtain.It is white solid, can directly use commercially available product, or uses after can being ground into micronized.
In addition, the compound that has a heat cross-linking functional group more preferably has the compound that does not need in fact the heat cross-linking of heat cross-linking promotor functional group.By not needing heat cross-linking promotor, the storage stability of resin combination is excellent.Specifically, can enumerate triazine based compound, benzoxazine based compound and blocked isocyanate based compound.
These compounds with heat cross-linking functional group also can mix use.Wherein, from the aspect of favorable dispersity, preferred trimeric cyanamide-isocyanuric acid affixture, triazine thiol glycol, three (2-hydroxyethyl) isocyanuric acid ester.
As benzoxazine based compound, the compound with benzoxazine ring that preferably uses following general formula (12) to represent.
(in formula (12), R 15that to have carbonatoms be the phenyl of 1～12 chain-like alkyl or replace the phenyl that has halogen for carbonatoms is 1～12 chain-like alkyl, carbonatoms is 3～8 cyclic alkyl, phenyl, replacement.In addition, on the ortho position of the carbon atom in the aromatic nucleus of Sauerstoffatom institute bonding and at least one the carbon atom in contraposition, bonding has hydrogen.)
R 15among, the example of the chain-like alkyl that is 1～12 as carbonatoms, can enumerate methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, and the example of the cyclic alkyl that is 3～8 as carbonatoms can be enumerated cyclopentyl, cyclohexyl.In addition, as replacement, to have carbonatoms be the phenyl of 1～12 chain-like alkyl or replace the phenyl that has halogen, can enumerate o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, adjacent ethylphenyl, an ethylphenyl, to ethylphenyl, o-tert-butyl phenyl, a tert-butyl-phenyl, to tert-butyl-phenyl, Chloro-O-Phenyl, o-bromophenyl etc.Wherein, due to good treatability, R can be provided 15more preferably methyl, ethyl, propyl group, phenyl, o-methyl-phenyl-.
As benzoxazine based compound, the compound that for example more preferably uses following general formula (13) to represent.
Figure BDA0000115023190000171
(in formula (13), R 16be preferably any in the divalent organic group that following formula group (14) represents.)-CH 2--CH 2CH 2--CH(CH 3) 2--CH 2(CH 3) 2--S--SO 2-(14)-O--CO-
As benzoxazine based compound, it can only consist of monomer, can be also a plurality of molecule aggregations and form oligopolymer state.In addition, can also use the benzoxazine compound with different structure simultaneously.Specifically, preferably use bis-phenol benzoxazine.
As epoxy based compound, can use various compound well known in the art.The epoxy equivalent (weight) of epoxy resin can suitably be selected from wide region, conventionally preferably uses the epoxy resin that epoxy equivalent (weight) is 100～10000, and particularly preferably using epoxy equivalent (weight) is 100～3000 epoxy resin.
As epoxy based compound, can preferably use the epoxy compounds in 1 molecule with more than 2 epoxy group(ing).As there is the epoxy compounds of more than 2 epoxy group(ing) in 1 molecule, for example, can enumerate the bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin; The phenolic resin varnish type epoxy resins such as phenol phenolic resin varnish, cresols phenolic resin varnish type epoxy resin, bisphenol type phenolic varnish; The epoxide of the various dicyclic pentylene modified resol that dicyclopentadiene reacted with various phenol and obtain.
In above-mentioned epoxy resin, from the aspect of the thermotolerance of heat-curing resin, solvent resistance, resistance to plating excellence, preferably bisphenol A type epoxy resin, phenolic resin varnish type epoxy resin, modified novolac type epoxy resin and dicyclopentadiene type epoxy resin.
As the goods more specifically of dicyclopentadiene type epoxy resin, can enumerate " " HP-7200 " that XD-1000 ”, DIC society manufactures etc. that Japanese chemical drug society manufactures.
As the goods more specifically of phenolic resin varnish type epoxy resin, can enumerate " " the Epiclon N-680 " that NC-7000L ”, DIC society manufactures etc. that Japanese chemical drug society manufactures.As the goods more specifically of modified novolac type epoxy resin, can enumerate " NC-3000 " that Japanese chemical drug society manufactures etc.These epoxy resin can be used alone, or two or more kinds in combination.
As required, the solidifying agent of can also blending epoxy in hot curing resin composition of the present invention using.As epoxy curing agent, be not particularly limited, as long as have, make epoxy resin cure or promote curing effect, just can use widely existing known or commercially available solidifying agent.As epoxy curing agent, specifically, except for example resol, imidazolium compounds, acid anhydrides, fatty amine, alicyclic polyamine, aromatic polyamine, tertiary amine, Dyhard RU 100, guanidine class or their epoxy addition or micro encapsulation beyond the region of objective existence, solidifying agent or all not limited uses of curing catalyst such as the organic phosphine based compounds such as triphenylphosphine, tetraphenylphosphonium, tetraphenyl borate salts, DBU or its derivative, can be separately or two or more be used in combination known habitual material.
While using these epoxy curing agents, its addition conventionally with respect to 100 weight part epoxy resin preferably at 0.01～200 weight part, particularly preferably in the scope of 0.1～100 weight part.
Blocked isocyanate refers to by making the isocyanic ester in molecule with 2 above isocyanate group react the compound obtaining with end-capping reagent.As isocyanic ester, can enumerate hexamethylene diisocyanate, 4, 4 '-diphenylmethanediisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, eylylene diisocyanate, 4, 4 '-dicyclohexyl methane diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, 4, 4 '-diphenyl diisocyanate, 1, two (isocyanato-methyl) hexanaphthenes of 3-, phenylene 1, 4-vulcabond, phenylene 2, 6-vulcabond, 1, 3, 6-hexa-methylene triisocyanate or hexamethylene diisocyanate etc.As end-capping reagent, use alcohols, phenols, ε-caprolactam, oximes, active methylene group class, thio-alcohol, amine, acid imide, amides, imidazoles, ureas, Carbamates, imines class or sulfites etc.
Goods more specifically as above-mentioned blocked isocyanate compounds, for example, being used as hexamethylene diisocyanate (following, also referred to as " HDI ") is trade(brand)name DURANATE17B-60PX, TPA-B80E, TPA-B80X, MF-B60X, E402-B80T, ME20-B80S, MF-K60X, the K6000 of chemistry society of the Asahi Chemical Industry manufacture of blocked isocyanate.In addition, as Mitsui Chemicals urethane society goods, commodity in use name Takenate B-882N, as tolylene diisocyanate be the trade(brand)name Takenate B-830 of blocked isocyanate, as 4,4 '-diphenylmethanediisocyanate is the trade(brand)name Takenate B-815N of blocked isocyanate, as the Takenate B-846N of two (isocyanato-methyl) the hexamethylene methane series blocked isocyanates of 1,3-.In addition, can enumerate trade(brand)name CORONETAP-M, 2503,2515,2507 that Japanese polyurethane industry society manufactures, 2513 or Millionate MS-50 etc., they can be used alone or in combination of two or more.
In addition, in order to show 200 ℃ of following curability at low temperatures, preferably use the blocked isocyanate of the HDI system that above-mentioned solidification value is low.
(C) resin combination
With respect to 100 mass parts polyimide, resin combination preferably contains the compound with heat cross-linking functional group in the scope of 1 mass parts～40 mass parts.If there is the compound of heat cross-linking functional group in the scope of 1 mass parts～40 mass parts, can not damage thermotolerance (scolding tin thermotolerance), low warpage properties, flexibility, thereby preferably.Wherein, if there is the compound of heat cross-linking functional group, be more than 5 mass parts, from the aspect of cross-linking density particularly preferably, if below 20 mass parts, from warpage and elastic aspect particularly preferably.Resin combination was preserved after 3 months, and the variation of viscosity is preferably below 20%.
Resin combination be preferably comprise acid number more than 16mgKOH/g to the polyimide precursor below 70mgKOH/g with there is the resin combination of the compound of heat cross-linking functional group, preserve after 1 month, the variation of viscosity is in 10%.More preferably, the acid number of polyimide is below 70mgKOH/g, does not produce reaction under storage temperature, preserves after 1 month being changed to below 10% of viscosity.If preserve being changed to below 10% of viscosity after 1 month, storage stability is excellent, is preferably used as the ink that can stablize printing.
Resin combination of the present invention preferably meets following condition: the Young's modulus after thermofixation is 0.3GPa～1.4GPa, in solder bath in 260 ℃ of dippings 60 seconds time without expanding, burning.Utilization meets the resin combination of these Young's modulus and the dip test in solder bath, can realize the resin combination that can provide excellent heat resistance after thermofixation and have the cured film of low warpage, low-resilience.Wherein, the Young's modulus after solidifying is 0.4GPa～1.0GPa more preferably, by making the resin combination that meets this characteristic, further demonstrates low warpage, low-resilience, but also meets thermotolerance.
Except polyimide precursor, have the compound of heat cross-linking functional group, resin combination can also contain fire retardant.Fire retardant is not particularly limited, yet from the viewpoint of environmental protection and the viewpoint of organism toxicity, is preferably the fire retardant of non-halogen based compound.The fire retardant that is as non-halogen, can enumerate P contained compound and inorganic combustion inhibitor etc.In resin combination, preferably halogen series elements content is below 1000ppm, has the flame retardant resistance of VTM-0 according to UL-94 standard.These fire retardants can be used a kind of, also can mix two or more uses.
For the P contained compound as fire retardant, can enumerate the phosphorus compounds such as phosphine nitrile, phosphine, phosphine oxide, phosphoric acid ester and phosphorous acid ester.Particularly, from the aspect of the consistency with polyimide compositions, preferably use phosphine nitrile, phosphine oxide or phosphoric acid ester.
For the inorganic combustion inhibitor as fire retardant, can enumerate antimony compounds and metal hydroxides etc.As antimony compounds, can enumerate ANTIMONY TRIOXIDE SB 203 99.8 PCT and antimony pentaoxide.As metal hydroxides, can enumerate aluminium hydroxide, magnesium hydroxide etc.
Addition to fire retardant is not particularly limited, and can suitably change according to the kind of used fire retardant.Conventionally, the content of polyimide of take is benchmark, preferably in the scope of 5 quality % to 50% quality, uses.
While using inorganic combustion inhibitor, because it is insoluble in organic solvent, so the particle diameter of its powder is preferably below 100 μ m.If the particle diameter of powder is below 100 μ m, easily sneak in polyimide compositions, can not damage the transparency of the resin after solidifying, thereby preferably.In addition in order to improve flame retardant resistance, the particle diameter of powder is preferably below 50 μ m, is particularly preferably below 10 μ m.
Except polyimide precursor, have the compound of heat cross-linking functional group, resin combination can also contain organic solvent.Can preferably use to be dissolved in after state in organic solvent is made varnish.As such organic solvent, can enumerate N,N-dimethylacetamide, N, N-diethyl acetamide, DMF, N, the acid amides series solvents such as N-diethylformamide, METHYLPYRROLIDONE; The lactone such as gamma-butyrolactone, γ-valerolactone series solvent; The sulfur-bearing such as dimethyl sulfoxide (DMSO), diethyl sulfoxide series solvent; The phenol such as cresols, phenol series solvent; The ester series solvents such as ether series solvent, butyl benzoate, ethyl benzoate, methyl benzoate such as diethylene glycol dimethyl ether (diglyme), TRIGLYME (triglyme), tetraethylene glycol dimethyl ether, dioxane, tetrahydrofuran (THF).Particularly, from the aspect of high boiling point and low water absorbable, can preferably use METHYLPYRROLIDONE, gamma-butyrolactone, triglyme, butyl benzoate, ethyl benzoate.In addition, they can use separately, also can share two or more.
While making coated film, according to its coating method, carry out viscosity and thixotropic adjustment.As required, use after also can adding filler or thixotropy imparting agent.In addition, can also add the additives such as known defoamer, flow agent.
While using resin combination to form film, can be printed on flexible printed circuit substrate or semiconductor wafer surface by known silk screen printing or precise glue dispensing method.
Resin composition for screen printing of the present invention is above-mentioned resin combination, and solid component concentration is more than 45%, by silk screen printing, on base material, to print, dry after, dry film thickness is more than 15 μ m, and spreads and sinks in that to ooze be below 40 μ m.If the solid component concentration of resin combination is more than 45%, easily obtain needed dry film thickness.If dry film thickness is more than 15 μ m, when printing and forming protective membrane, on circuit, obtain sufficient thickness on circuit substrate, reliability is excellent.In addition, if spreading and sinking in after film generation oozed, be below 40 μ m, the precision of printing improves, and the resolving power of the protective membrane after patterning is high.
In resin combination, the imidization reaction of polyimide can fully realize at 150 ℃～220 ℃.Therefore,, though also depend on coating film thickness, can utilize baking oven or hot-plate to make top temperature is the scope of 150 ℃～220 ℃, heats 5 minutes～100 minutes, thereby carry out desolventizing under the inert atmospheres such as air or nitrogen.Can in the whole treatment time, be constant temp, Yi Bian Yi Bian also can heat up and process at leisure.
Resin combination demonstrates excellent thermotolerance by thermofixation, and therefore surface cure film, interlayer dielectric, bonding sheet or the use in printed circuit board protection insulating film as semiconductor element is useful, can be suitable for various electronic units.In addition, as the surface protection film with the tellite of electronic circuit, resin combination can be used aptly.For example, as flexible tellite, use ESPANEX M (chemistry society of Nippon Steel manufactures) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)), a part of coating resin composition on this circuit substrate.Then, for uncoated part, implement electronickelling gold, thereby use.Surface protection film has been given play to good insulation characterisitic.
In addition; use the two sides copper foil laminate of ESPANEX M (chemistry society of Nippon Steel manufactures) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)) to make two face component mounting circuit substrates; position printing resin composition beyond the parts installation portion of this circuit substrate also solidifies; when resin combination is used as to surface protection film, also given play to good insulation characterisitic.Herein, the thickness of surface protection film is preferably 1 μ m～50 μ m.Thickness is 1 μ m when above, processes easily, is 50 μ m when following, easily bending, easily insertion.
Below, by embodiment and the comparative example carrying out for effect clearly of the present invention, illustrate the present invention, but the present invention is not limited to following embodiment and comparative example.
(1) evaluation of polyimide precursor
(mensuration of imide rate)
Imide rate is obtained by IR method.With 1480cm -1near the peak based on phenyl ring be benchmark, by with 1380cm -1near the ratio of the absorbancy at the peak generating based on imide ring is obtained imide rate.Before and after these peaks, to link the mode of the Gu Hegu at peak, suitably mark baseline, the height that the summit from each peak is fallen to the line of its baseline and the intersection point of baseline to peak is defined as each absorbancy.With composition separately at 50 ℃ of synthesis of polyimides precursors, and 80 ℃ dry, by polyimide precursor now at 1480cm -1the absorbancy at place is made as A1, by 1380cm -1absorbancy be made as B1.In addition, by air atmosphere in 220 ℃ of thermal treatments the polyimide precursor after 60 minutes at 1480cm -1the absorbancy at place is made as A2,1380cm -1absorbancy be made as B2, the 1480cm under arbitrary temp -1absorbancy be made as A3,1380cm -1absorbancy be made as B3, now, the imide rate in the time of 60 minutes 220 ℃ of thermal treatments of take is 100, and the imide rate C under arbitrary temp obtains by following formula: and imide rate C=((B3/A3-B1/A1)/(B2/A2-B1/A1)) * 100 (%).
(weight-average molecular weight mensuration)
Weight-average molecular weight is measured under the following conditions by gel permeation chromatography (GPC).As solvent, use N, dinethylformamide (manufacture with the pure pharmaceutical worker's industry of light society, high performance liquid chromatography with), is used and before mensuration, adds and have the lithiumbromide of 24.8mmol/L monohydrate the solvent of the phosphoric acid (manufacture with the pure pharmaceutical worker's industry of light society, high performance liquid chromatography use) of (manufacture with the pure pharmaceutical worker's industry of light society, purity 99.5%) and 63.2mmol/L.In addition, for calculating the calibration curve of weight-average molecular weight, use polystyrene standard (Dong Caoshe manufacture) to make.
Post: Shodex KD-806M (manufacture of Zhao He electrician society), TSK-GEL SUPER HM-H (Dong Caoshe manufacture)
Flow velocity: 1.0mL/ minute
Column temperature: 40 ℃
Pump: PU-2080Plus (manufacture of JASCO society)
Detector: RI-2031Plus (RI: differential refractometer, JASCO society manufacture)
UV-2075Plus (UV-VIS: UV, visible light absorptiometer, JASCO society manufacture)
(mensuration of acid number)
The polyimide varnish that the about 2g of accurate weighing is synthetic, after diluting with 40g gamma-butyrolactone (manufacture with the pure pharmaceutical worker's industry of light society, superfine) and 10g ethanol (manufacture with the pure pharmaceutical worker's industry of light society, superfine), according to JIS K 0070-1966, use 0.1mol/L ethanol potassium hydroxide solution for automatic titration device (Mitsubishi Chemical analytical technology society manufactures, GT-100) (with the pure pharmaceutical worker's industry of light society manufacture, volumetry with) carry out titration.Be converted into polyimide purity, measure acid number.
(HAST test evaluation)
HAST (Highly Accelerated Temperature and Humidity Stress Test, high acceleration temperature, humidity, stress test) test evaluation is implemented as follows.Copper wiring case (being formed with the insulation layer from polyimide precursor thereon) about the comb teeth-shaped of test wire substrate, between the broach of live width/line-spacing (line/space)=30 μ m/30 μ m, apply the voltage of 5V, 130 ℃, the hot and humid lower placement of 85%RH.After 96 hours, measure the insulation resistance between broach.
(2) evaluation of resin combination
(storage stability)
As the evaluation of storage stability, measure the variation of weight-average molecular weight (Mw) and the variation of viscosity.Resin combination is preserved after 1 month in the freezer of-20 ℃, and being changed to of weight-average molecular weight (Mw) is 10% good with zero expression when following, while surpassing 10% with * represent defective, viscosity be changed to 10% when following, good with zero expression, while surpassing 10%, with * represent defective.
(viscosimetric analysis)
In Brookfield viscometer (manufacture of Dong Ji industry society, RE-85R), with the mensuration temperature of 23 ℃, utilize cone rotor (05,3 ° * R12 of rotor numbering) to measure viscosity.
(weight-average molecular weight mensuration)
Similarly measure with the project that in the evaluation of above-mentioned (1) polyimide precursor, weight-average molecular weight is measured.
(3) evaluating characteristics of cured film
(making of cured film)
Utilize scraping strip coating machine coating resin composition on substrate, at room temperature carry out 5 minutes～10 minutes levellings, utilize hot-air oven 120 ℃ of heating 30 minutes, next, 180 ℃ of heating 60 minutes, carry out dry solidification.As substrate, KAPTON (registered trademark) 100EN that uses society of Dong Li-Du Pont to manufacture, is coated with at its one side, with above-mentioned same condition under after levelling, dry solidification, as sample for following test.Thickness after dry solidification is approximately 20 μ m.
(warpage evaluation)
Under 23 ℃, the environment of humidity 50%, said sample is cut into 5cm * 5cm, as warpage, measure the distance that float with respect to central part in bight.Warpage is that the sample below 10mm is good with zero expression, for the sample below 5mm with ◎, represent better, the sample that surpasses 10mm with * represent defective.
(rebound resilience evaluation)
Under 23 ℃, the environment of humidity 50%, use said sample, lamination is had to a side direction inner bending of cured film, with parallel plate clamping, and be increased in gradually the load applying between parallel plate, after 1 minute, measure the load while maintaining with radius of curvature R=0.5mm.Load when being only KAPTON 100EN substrate, it is 10% good with zero expression when following that load increases to, be 5% with ◎, represent when following better, over 10%, screen resilience when high with * represent defective.
(Evaluation of Heat Tolerance)
Said sample is cut into 3cm * 3cm, in solder bath in 260 ℃ dipping 60 seconds, carry out thermal test.According to JPCA-BM02 standard, film surface do not observe expansion, burn etc. is evaluated as zero when abnormal, have when abnormal to be evaluated as *.
(chemical proofing evaluation)
Said sample is cut into 80mm * 180mm and make test film, carry out chemical proofing evaluation.In 23 ℃, in the aqueous sodium hydroxide solution of 10 quality %, flood 15 minutes, measure the changes in weight before and after dipping, and divided by the weight of the KAPTON as substrate, calculate weight decrement.Weight decrement is 10% good with zero expression when following, be 4% with ◎, represent when following better, while surpassing 10% with * represent defective.
(flame retardant resistance evaluation)
The sample of two sided coatings is cut into 200mm * 50mm, and being rolled into length is the tubular that 200mm, diameter are 12.7mm, uses it as the metewand of flame retardant resistance, according to the testing vertical flammability of stipulating in the UL-94 of U.S. UL standard, evaluates.
(second-order transition temperature (Tg) mensuration)
As substrate, use Copper Foil (18 μ m) (F2-WS Furukawa Circuit Foil Co., Ltd. manufactures), on this substrate with the above-mentioned cured film that similarly forms.Resulting laminate is impregnated in iron(ic) chloride (III) aqueous solution (40 Baumes, He Jiancaoda society manufacture) and carries out etching, only obtain solidifying film layer.After etching, under 23 ℃ of temperature, humidity 50% condition, after standing diel, carry out the mensuration of second-order transition temperature and Young's modulus.
About second-order transition temperature (Tg), use heat-stress-deformation measurement device (TMA/SS6100, セ イ コ mono-イ Application ス Star Le メ Application ト Na ノ テ Network ノ ロ ジYi society manufacture), under nitrogen atmosphere, (flow velocity 250cc/ minute) be take the condition that measurement range is 30 ℃～200 ℃ and measured Tg.
(elastic modulus detection)
By above-mentioned, only there is the sample shear of solidifying film layer to be cut into 5mm * 100mm, make test film.Utilize tensile testing machine (RTG-1210/A& D Co., LTD manufactures) measure resulting test film, thus obtain Young's modulus.
(elongation mensuration)
By above-mentioned, only there is the sample shear of solidifying film layer to be cut into 5mm * 100mm, make test film.Utilize tensile testing machine (RTG-1210/A& D Co., LTD manufactures) measure resulting test film, thus obtain elongation.Elongation is 10% with △, to represent well when above, is 30% further good with zero expression when above, be 50% with ◎, represent when above better, while being less than 10% with * represent defective.
[synthesis example 1: polyimide precursor synthetic]
To being provided with in three mouthfuls of removable flasks of stirrer, nitrogen ingress pipe, thermometer, add polytetramethylene ether two para-amino benzoic acid esters (PMAB) (IHARA CHEMICAL INDUSTRY CO., LTD. manufacture, trade(brand)name: ELASMER 1000, weight-average molecular weight 1305) 65.25g, 1,3-two (3-amino-benzene oxygen) benzene (APB) 14.62g, gamma-butyrolactone 320g, be at room temperature stirred to formation homogeneous solution.Next, add 4, two Tetra hydro Phthalic anhydride (ODPA) 29.47g of 4 '-oxygen and Tetra hydro Phthalic anhydride 1.48g, import nitrogen, and ice-cold lower stirring 1 hour, stirs 6 hours at 50 ℃ thereafter.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[embodiment 1]
By the polyimide precursor obtaining in synthesis example 1, further 180 ℃ of heating, the mode that the imide rate of take is 51% makes its part imidization.Wherein, (following as the compound with heat cross-linking functional group to adding 20 mass parts in 100 mass parts polyimide precursors, be called " thermal cross-linking agent ") methylolation trimeric cyanamide NIKALACMW-390 (SANWA CHEMICAL CO., LTD manufactures), the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.Evaluation result is listed in following table 1.
[embodiment 2～embodiment 5]
As shown in table 1, making the imide rate of polyimide precursor and thermal cross-linking agent is material shown in following table 1, changes as described in Table 1 imide rate, in addition obtains similarly to Example 1 cured film.Evaluation result is listed in following table 1.It should be noted that, the linking agent of recording in following table 1 is below shown.
Bis-F: bis-phenol benzoxazine (manufacture of little Xi chemical industry society, Bis-F type benzoxazine)
TPA-B: the blocked polyisocyanates of hexamethylene diisocyanate (manufacture of chemistry society of Asahi Chemical Industry, DURANATE TPA-B80E)
[embodiment 6]
The content of PMAB in whole diamines is changed to 35mmol by 50mmol, the content of APB is changed to 65mmol by 50mmol, making imide rate is 51%, in addition obtains similarly to Example 1 cured film.Evaluation result is listed in following table 1.
[embodiment 7]
When synthetic, do not add Tetra hydro Phthalic anhydride, and change as described in Table 1 imide rate, in addition obtain similarly to Example 1 cured film.Evaluation result is listed in following table 1.
[comparative example 1]
The content that the content of PMAB in whole diamines is changed to 20mmol, APB changes to 80mmol, and does not add thermal cross-linking agent, and in addition other formulas wait and carry out similarly to Example 2, obtain cured film.Evaluation result is listed in following table 2.
[comparative example 2]
The content that the content of PMAB in whole diamines is changed to 65mmol, APB changes to 35mmol, and does not add thermal cross-linking agent, and in addition other formulas wait and carry out similarly to Example 2, obtain cured film.Evaluation result is listed in following table 2.
[comparative example 3]
Except not adding thermal cross-linking agent, other formulas wait and carry out similarly to Example 2, obtain cured film.Evaluation result is listed in following table 2.
[comparative example 4]
Except imide rate is changed to 38%, obtain similarly to Example 1 cured film.Evaluation result is listed in table 2.
[table 1]
Figure BDA0000115023190000271
[table 2]
Figure BDA0000115023190000281
As shown in table 1, table 2, the imide rate of polyimide precursor is (embodiment 1～embodiment 7) below 98% and in the situation that contains thermal cross-linking agent, meets warpage evaluation, rebound resilience evaluation, Evaluation of Heat Tolerance, elongation evaluation, chemical proofing evaluation.In addition,, if known imide rate is in 40%～98% scope, demonstrate good storage stability.On the other hand, imide rate is less than in 40% situation (comparative example 4) or not containing (comparative example 1～comparative example 3) in the situation of thermal cross-linking agent, cannot obtains the balance of the various characteristics of warpage, rebound resilience, heat-resistant agent, elongation, chemical proofing.
[synthesis example 2: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 40.0g, 1, two (3-amino-benzene oxygen) benzene (APB) 8.77g of 3-, gamma-butyrolactone 130g, toluene 20g, γ-valerolactone 1.2g, pyridine 1.8g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 30.61g.Stir after 0.5 hour, be warming up to 170 ℃, heat 2 hours.System is cooled to after 100 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 8.77g of 1,3-.After 5 hours, add Tetra hydro Phthalic anhydride 1.48g, be cooled to room temperature.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[synthesis example 3: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 40g, 1,3-two (3-amino-benzene oxygen) benzene (APB) 14.033g, gamma-butyrolactone (GBL) 43g, ethyl benzoate (BAEE) 43g, toluene 20g, γ-valerolactone 1.2g, pyridine 1.8g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 14.32g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 18.365g.Stir after 0.5 hour, be warming up to 170 ℃, heat 4 hours.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Remove after water byproduct, stop refluxing, remove whole toluene.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 3.508g of 1,3-.After 5 hours, add Tetra hydro Phthalic anhydride 0.889g, be cooled to room temperature.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[synthesis example 4: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 40g, gamma-butyrolactone (GBL) 43g, ethyl benzoate (BAEE) 43g, toluene 20g, γ-valerolactone 1.2g, pyridine 1.8g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 14.32g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 18.365g.Stir after 0.5 hour, be warming up to 170 ℃, heat 4 hours.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Remove after water byproduct, stop refluxing, remove whole toluene.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 17.542g of 1,3-.After 5 hours, add Tetra hydro Phthalic anhydride 0.889g, be cooled to room temperature.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[embodiment 8]
In polyimide precursor 100 mass parts that obtain in synthesis example 2, add bis-phenol benzoxazine (manufacture of Bis-F type benzoxazine little Xi chemical industry society) 5 mass parts as thermal cross-linking agent, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 9]
In polyimide precursor 100 mass parts that obtain, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society, monomer flame retardant resistance evaluate zero) 10 mass parts as thermal cross-linking agent in synthesis example 3.As fire retardant, add phosphine nitrile flame retardant (following general formula (15)) 15 mass parts, magnesium hydroxide (average aggregate particle size 1.0 μ m, Tateho Chemical Industries Co., Ltd. manufacture) 20 mass parts, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
Figure BDA0000115023190000301
[embodiment 10]
In polyimide 100 mass parts that obtain, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society, monomer flame retardant resistance evaluate zero) 10 mass parts as thermal cross-linking agent in synthesis example 4.As fire retardant, add phosphine nitrile flame retardant (following general formula (15)) 15 mass parts, magnesium hydroxide (average aggregate particle size 1.0 μ m, Tateho Chemical Industries Co., Ltd. manufacture) 20 mass parts, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.Embodiment 8～embodiment 10 the results are shown in following table 3.
[table 3]
Figure BDA0000115023190000311
As shown in table 3, in the situation that containing JEFFAMINE and thermal cross-linking agent, meet warpage evaluation, rebound resilience evaluation, thermotolerance, flame retardant resistance evaluation, elongation, chemical proofing (embodiment 8～embodiment 10).
[synthesis example 5: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 20.0g, JEFFAMINE ED-600 (manufacture of Huntsman company, weight-average molecular weight 600) 18.0g, 1, two (3-amino-benzene oxygen) benzene (APB) 11.110g of 3-, gamma-butyrolactone 130g, toluene 20g, γ-valerolactone 1.2g, pyridine 1.8g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 14.32g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 17.721g.Stir after 0.5 hour, be warming up to 170 ℃, heat 2 hours.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 3.508g of 1,3-.After 5 hours, add Tetra hydro Phthalic anhydride 1.481g, be cooled to room temperature.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[synthesis example 6: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 20.0g, JEFFAMINE ED-600 (manufacture of Huntsman company, weight-average molecular weight 600) 18.0g, 1, two (3-amino-benzene oxygen) benzene (APB) 8.771g of 3-, gamma-butyrolactone 130g, toluene 20g, γ-valerolactone 1.2g, pyridine 1.8g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 14.32g and 4, two Tetra hydro Phthalic anhydride (ODPA) 17.062g of 4 '-oxygen.Stir after 0.5 hour, be warming up to 170 ℃, heat 2 hours.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 5.847g of 1,3-.After 5 hours, add Tetra hydro Phthalic anhydride 1.481g, be cooled to room temperature.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[synthesis example 7: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 40.0g, gamma-butyrolactone 130g, toluene 20g, γ-valerolactone 1.2g, pyridine 1.8g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 19.332g and 4, two Tetra hydro Phthalic anhydride (ODPA) 12.409g of 4 '-oxygen.Stir after 0.5 hour, be warming up to 170 ℃, heat 2 hours.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 16.08g of 1,3-.After 5 hours, add aniline 0.931g, be cooled to room temperature.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[synthesis example 8: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 18.6g, JEFFAMINE ED-600 (manufacture of Huntsman company, weight-average molecular weight 600) 16.74g, 1, two (3-amino-benzene oxygen) benzene (APB) 12.133g of 3-, gamma-butyrolactone 130g, toluene 20g, γ-valerolactone 1.2g, pyridine 1.8g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 14.32g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 19.332g.Stir after 0.5 hour, be warming up to 170 ℃, heat 3 hours.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 1.462g of 1,3-.After 5 hours, be cooled to room temperature.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[synthesis example 9: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 18.2g, JEFFAMINE ED-600 (manufacture of Huntsman company, weight-average molecular weight 600) 16.38g, 1, two (3-amino-benzene oxygen) benzene (APB) 12.77g of 3-, gamma-butyrolactone 130g, toluene 20g, γ-valerolactone 1.2g, pyridine 1.8g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 14.32g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 19.332g.Stir after 0.5 hour, be warming up to 170 ℃, heat 3 hours.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 0.532g of 1,3-.After 5 hours, be cooled to room temperature.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[synthesis example 10: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE ED-900 (manufacture of Huntsman company, weight-average molecular weight 900) 36.0g, 1, two (3-amino-benzene oxygen) benzene (APB) 12.279g of 3-, are stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 14.32g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 17.721g.Stir after 0.5 hour, be warming up to 170 ℃, heat 2 hours.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 5.262g of 1,3-.After 5 hours, add Tetra hydro Phthalic anhydride 1.481g, be cooled to room temperature.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[synthesis example 11: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE D-2000 (manufacture of Huntsman company, weight-average molecular weight 2000) 40.0g, 1, two (3-amino-benzene oxygen) benzene (APB) 18.126g of 3-, are stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 14.32g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 17.721g.Stir after 0.5 hour, be warming up to 170 ℃, heat 2 hours.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 5.262g of 1,3-.After 5 hours, add Tetra hydro Phthalic anhydride 1.481g, be cooled to room temperature.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[synthesis example 12: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE D-400 (manufacture of Huntsman company, weight-average molecular weight 2000) 32.0g, 1, two (3-amino-benzene oxygen) benzene (APB) 0.585g of 3-, are stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 14.32g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 17.721g.Stir after 0.5 hour, be warming up to 170 ℃, heat 2 hours.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 5.262g of 1,3-.After 5 hours, add Tetra hydro Phthalic anhydride 1.481g, be cooled to room temperature.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[synthesis example 13: polyimide synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 40.0g, 1, two (3-amino-benzene oxygen) benzene (APB) 16.08g of 3-, gamma-butyrolactone 130g, toluene 20g, γ-valerolactone 1.2g, pyridine 1.8g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 16.11g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 17.721g.Stir after 0.5 hour, be warming up to 170 ℃, heat 5 hours.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide.
[synthesis example 14: polyimide precursor synthetic]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 35.0g, gamma-butyrolactone 130g, toluene 20g, γ-valerolactone 1.2g, pyridine 1.8g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 19.332g and 4, two Tetra hydro Phthalic anhydride (ODPA) 12.409g of 4 '-oxygen.Stir after 0.5 hour, be warming up to 170 ℃, heat 2 hours.System is cooled to after 60 ℃, adds JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 5.0g and two (3-amino-benzene oxygen) benzene (APB) 16.08g of 1,3-.After 5 hours, add aniline 0.931g, be cooled to room temperature.In reaction, for water byproduct, with methylbenzene azeotropic, use the spherical condensation tube that possesses moisture separated and collected device to dewater under refluxing.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain polyimide precursor.
[embodiment 11]
In polyimide precursor 100 mass parts that obtain in synthesis example 5, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society) 15 quality as thermal cross-linking agent, the polyimide of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 12]
In polyimide precursor 100 mass parts that obtain, add methylolation trimeric cyanamide (the MW-390:NIKALAC MW-390SANWA CHEMICAL CO. as thermal cross-linking agent in synthesis example 5, LTD manufactures) 20 mass parts, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 13]
In polyimide precursor 100 mass parts that obtain in synthesis example 5, add blocked polyisocyanates as the hexamethylene diisocyanate of thermal cross-linking agent (chemistry society of TPA-B:DURANATE TPA-B80E Asahi Chemical Industry manufactures) 20 mass parts, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 14]
In polyimide precursor 100 mass parts that obtain, add epoxy resin (manufacture of dicyclopentadiene type epoxy resin HP7200 ,DIC society) 24 mass parts and epoxy resin amine adduct (AJICURE PN-23, Ajinomoto Fine-Techno Co. as thermal cross-linking agent in synthesis example 5, Inc. manufacture) 0.8 mass parts, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 15]
In polyimide precursor 100 mass parts that obtain in synthesis example 6, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society) 10 mass parts as thermal cross-linking agent, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 16]
In polyimide precursor 100 mass parts that obtain in synthesis example 7, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society) 10 mass parts as thermal cross-linking agent, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 17]
In polyimide precursor 100 mass parts that obtain in synthesis example 8, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society) 15 mass parts as thermal cross-linking agent, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 18]
In polyimide precursor 100 mass parts that obtain in synthesis example 9, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society) 15 mass parts as thermal cross-linking agent, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 19]
In polyimide precursor 100 mass parts that obtain in synthesis example 10, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society) 15 mass parts as thermal cross-linking agent, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 20]
In polyimide precursor 100 mass parts that obtain in synthesis example 11, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society) 15 mass parts as thermal cross-linking agent, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[embodiment 21]
In polyimide precursor 100 mass parts that obtain in synthesis example 12, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society) 15 mass parts as thermal cross-linking agent, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.Embodiment 11～embodiment 19 the results are shown in following table 4, and embodiment 20～embodiment 21 the results are shown in following table 5.It should be noted that, in following table 4, be epoxy 1 by above-mentioned epoxy resin and above-mentioned epoxy resin amine adduct brief note.
[comparative example 5]
In polyimide 100 mass parts that obtain in synthesis example 13, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society) 15 mass parts as thermal cross-linking agent, the polyimide of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.
[comparative example 6]
In polyimide precursor 100 mass parts that obtain in synthesis example 5, add thermal cross-linking agent and following acrylate mixture, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.Consisting of of acrylate mixture: propenoic methyl carbamate (manufacture of You society, BLEMMERDP403AU) 40 mass parts, dipentaerythritol acrylate (chemistry society of common prosperity society manufactures) 16 mass parts, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester (manufacture of the synthetic society in East Asia, M-5710) 3.3 mass parts, polyester acrylate (East Asia is synthesized society and manufactured M-6100) 6.7 mass parts.
[comparative example 7]
In polyimide precursor 100 mass parts that obtain in synthesis example 14, add bis-phenol benzoxazine (manufacture of Bis-F:Bis-F type benzoxazine little Xi chemical industry society) 10 mass parts as thermal cross-linking agent, the polyimide precursor of take is concocted resin combination as the mode of 30 quality %.Make cured film, it is evaluated.Comparative example 5～comparative example 7 the results are shown in following table 5.
[table 4]
[table 5]
As shown in table 4 and table 5, imide rate is below 98% and in the situation that contains JEFFAMINE and thermal cross-linking agent, meets warpage evaluation, rebound resilience evaluation, Evaluation of Heat Tolerance (embodiment 11～embodiment 21).On the other hand, imide rate surpasses in 98% situation (comparative example 5), cannot obtain the balance of the various characteristics of warpage, rebound resilience, thermotolerance, chemical proofing.In addition, use in the situation of acrylate mixture as thermal cross-linking agent (comparative example 6), cannot obtain the balance of the various characteristics of warpage, rebound resilience, thermotolerance, pharmaceutical chemicals patience.In addition, imide rate is less than in 40% situation (comparative example 7), cannot obtain the balance of the various characteristics of warpage, rebound resilience, thermotolerance, pharmaceutical chemicals patience.
[embodiment 22]
(evaluation of the protective membrane of tellite)
Base material as flexible printed circuit board, use ESPANEX M (chemistry society of Nippon Steel manufactures) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)), producing live width/line-spacing is the comb shape running board of 30 μ m/30 μ m, 50 μ m/50 μ m, 100 μ m/100 μ m, 200 μ m/200 μ m.Resin combination to the part coating embodiment 11～embodiment 16 on this circuit substrate, uncoated part is implemented to electronickelling gold, the thickness that makes nickel is that the thickness of approximately 5 μ m, gold is approximately 0.05 μ m, and result is confirmed and is plated on the slipping into of part that has been coated with resin combination and is less than 20 μ m by MICRO-BEAM XRF ANALYSIS.In addition, by ohmer, confirmed that the state of insulation between circuit is good.In addition, at the comb shape portion printing-ink of comb shape running board, under DC50V, 85 ℃, the condition of humidity 85%, place 1000 hours, implement to measure the reliability test of resistance simultaneously, result all remains and surpasses 10 9the resistance of Ω, obtains good result.In addition, at the comb shape portion printing-ink of comb shape running board, under DC5V, 130 ℃, the condition of humidity 85%, place 96 hours, implement to measure the reliability test of resistance simultaneously, result all remains and surpasses 10 8the resistance of Ω, obtains good result.
In addition, use the two sides copper foil laminate of ESPANEX M (chemistry society of Nippon Steel manufactures) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)), making diameter is the carbon dioxide laser via hole of 100 μ m, makes two face component mounting circuit substrates after copper facing.Coating resin composition beyond the parts installation portion of this circuit substrate, utilizes soldering paste that parts are fixed on after uncoated portion, utilizes the IR reflow stove of 260 ℃ to carry out parts installation, and ink pellet surface, circuit part do not observe extremely.In addition, by crooked 180 degree of the non-installation portion of parts, insert in electronics, under 85 ℃, the environment of humidity 85%, DC50V, worked well more than 1000 hours.
[embodiment 23]
(utilizing the formation of the protective membrane of silk screen print method patterning)
Use the two sides copper foil laminate of ESPANEX M (chemistry society of Nippon Steel manufactures) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)), making diameter is the carbon dioxide laser via hole of 100 μ m, makes two face component mounting circuit substrates after copper facing.Printing resin composition beyond the parts installation portion of this circuit substrate, the protective membrane of 17 μ m of formation patterning.The resolving power of protective membrane is good, and spreading and sinking in, to ooze be below 40 μ m.In addition, utilize soldering paste that parts are fixed on after uncoated portion (0.4mm * 0.3mm), utilize the IR reflow stove of 260 ℃ to carry out parts installation, the bonding strength of parts and circuit substrate and conducting are not observed extremely.In addition, ink pellet surface, circuit part do not observe extremely.In addition, by crooked 180 degree of the non-installation portion of parts, insert in electronics, under 85 ℃, the environment of humidity 85%, DC50V, worked well more than 1000 hours.
[embodiment 24]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 400g, 1,3-two (3-amino-benzene oxygen) benzene (APB) 140.33g, gamma-butyrolactone (GBL) 430g, ethyl benzoate (BAEE) 430g, toluene 80g, γ-valerolactone 12g, pyridine 18g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 143.2g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 183.65g.Stir after 0.5 hour, be warming up to 170 ℃, heat 4 hours.In reaction, for water byproduct, use the spherical condensation tube that possesses moisture separated and collected device, by the azeotropic with toluene, under refluxing, dewater.Remove after water byproduct, stop refluxing, remove whole toluene.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 35.08g of 1,3-.After 5 hours, add Tetra hydro Phthalic anhydride 8.89g, be cooled to room temperature.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain the varnish that polyimide precursor content is 52 quality % (solid component concentration is 52wt%).The resulting polyimide precursor of take is concocted as the mode of 30 quality %, makes cured film, and it is evaluated.
[embodiment 25]
On three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture separated and collected device.0 ℃ of ice-water bath, add JEFFAMINE XTJ-542 (manufacture of Huntsman company, weight-average molecular weight 1000) 400g, gamma-butyrolactone (GBL) 430g, ethyl benzoate (BAEE) 430g, toluene 80g, γ-valerolactone 12g, pyridine 18g, be stirred to evenly.In addition, add bit by bit 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) 143.2g and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) 183.65g.Stir after 0.5 hour, be warming up to 170 ℃, heat 4 hours.In reaction, for water byproduct, use the spherical condensation tube that possesses moisture separated and collected device, by the azeotropic with toluene, under refluxing, dewater.Remove after water byproduct, stop refluxing, remove whole toluene.System is cooled to after 60 ℃, adds two (3-amino-benzene oxygen) benzene (APB) 175.42g of 1,3-.After 5 hours, add Tetra hydro Phthalic anhydride 8.89g, be cooled to room temperature.Next with the strainer of 5 μ m, product is carried out to pressure filtration, thereby obtain the varnish that polyimide precursor content is 52 quality % (solid component concentration is 52wt%).The resulting polyimide precursor of take is concocted as the mode of 30 quality %, makes cured film, and it is evaluated.
[comparative example 8]
When synthetic, do not add JEFFAMINE XTJ-542, and to make the addition of two (3-amino-benzene oxygen) benzene (APB) of 1,3-be 283.59g, in addition carry out similarly to Example 24.
[comparative example 9]
When synthetic by 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is replaced by (TMEG) 397.5g of ethylene glycol bis (trimellitic acid 1,2-anhydride ester), in addition carries out similarly to Example 24.
[comparative example 10]
When synthetic, do not add two (3-amino-benzene oxygen) benzene (APB) of 1,3-, and the addition of JEFFAMINE XTJ-542 is replaced by 1000g, in addition carry out similarly to Example 24.Embodiment 24 to embodiment 25 and comparative example 8 are to the following table 6 of the results are shown in of comparative example 10.
[table 6]
As shown in table 6, the polyimide precursor that does not add the diamines of the dicarboxylic anhydride that has the dicarboxylic anhydride of ester group and used ad hoc structure and two kinds of ad hoc structures has met solvent soluble (storage stability), warpage evaluation and insulated electro resistive (HAST test) (embodiment 24～embodiment 25).On the other hand, do not contain the dicarboxylic anhydride of ad hoc structure polyimide precursor (comparative example 9), do not contain the balance that any one polyimide precursor (comparative example 8, comparative example 10) in the diamines of two kinds of ad hoc structures cannot be obtained the various characteristics of solvent soluble (storage stability), warpage evaluation, insulated electro resistive (HAST test).
Industrial applicibility
Resin combination of the present invention can provide demonstration more excellent stable on heating cured film by carrying out thermofixation; excellent heat resistance, the warpage of this cured film are few, resilience is low; therefore surface protection film, interlayer dielectric or the use in printed circuit board protection insulating film as semiconductor element is useful, can be suitable for various electronic units.
The Japanese Patent Application 2009-296969 that the Japanese Patent Application 2009-223843 that the Japanese Patent Application 2009-142935 submitting in the Japanese Patent Application 2009-138076 that the application submitted to based on June 9th, 2009, on June 16th, 2009, on September 29th, 2009 submit to and on December 28th, 2009 submit to.Its content all comprises in this application.

Claims (29)

1. a resin combination, it contains the compound that has the polyimide precursor of polyether structure and have heat cross-linking functional group, it is characterized in that, and the imide rate of described polyimide precursor is more than 40% below 98%;
The polyimide portion that described polyimide precursor comprises the structure with following general formula (1),
Figure FDA0000369142900000011
In formula (1), Z 1and Z 2represent 4 valency organic groups; R 1, R 2, R 3, R 4and R 5represent the alkylidene group that carbonatoms is 1～5, and there is or do not have side chain; M, n and q represent 1～50 integer;
In whole diamines in described polyimide precursor, the content of diamines with the structure of following general formula (2) be 15 % by mole above below 85 % by mole,
In formula (2), R 1, R 2, R 3, R 4and R 5represent the alkylidene group that carbonatoms is 1～5, and there is or do not have side chain; M, n and q represent 1～50 integer;
Described polyimide precursor comprises the polyamic acid portion with polyamic acid structure and the polyimide portion with polyimide structures, compare with described polyamic acid portion, in described polyimide portion, contain the diamines described in more with the structure of general formula (2).
2. resin combination as claimed in claim 1, is characterized in that, the imide rate of described polyimide precursor is more than 40% below 95%.
3. resin combination as claimed in claim 1, is characterized in that, in the diamines of the described structure with general formula (2), and R 2, R 3, R 4and R 5the alkylidene group representing is two or more alkylidene group.
4. as claim 1 or resin combination claimed in claim 3, it is characterized in that, described in there is general formula (2) the weight-average molecular weight of diamines of structure in 400 to 2000 scope.
5. resin combination as claimed in claim 4, is characterized in that, described in there is general formula (2) the weight-average molecular weight of diamines of structure in 600 to 2000 scope.
6. resin combination as claimed in claim 1, is characterized in that, the Z of described general formula (1) 1and Z 2for 4 valency organic groups of following general formula (3) expression,
In formula (3), R 17expression-O-,-SO 2-or-CO-.
7. resin combination as claimed in claim 1, it is characterized in that, the imide rate of described polyimide precursor is more than 50%, and imide rate D% and 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride meets the relational expression of E≤0.6D-30 with respect to the relation between content E % by mole of all acid composition.
8. resin combination as claimed in claim 1, is characterized in that, the Z of described general formula (1) 1and Z 2by from 3,3 ', 4, in 4 '-sulfobenzide tetracarboxylic dianhydride, remove 4 valency organic group residues after dicarboxylic anhydride structure and from 3,3 ', 4, the 4 valency organic group residues of removing in 4 '-benzophenone tetracarboxylic dianhydride after dicarboxylic anhydride structure form.
9. resin combination as claimed in claim 1, is characterized in that, the Z of described general formula (1) 1and Z 2by from 3,3 ', 4, in 4 '-sulfobenzide tetracarboxylic dianhydride, remove 4 valency organic group residues after dicarboxylic anhydride structure and from 4, the 4 valency organic group residues of removing after dicarboxylic anhydride structure in the two Tetra hydro Phthalic anhydrides of 4 '-oxygen form.
10. resin combination as claimed in claim 1, is characterized in that, comprises the polyimide portion of the structure with following general formula (4) in described polyimide precursor,
Figure FDA0000369142900000022
In formula (4), Z 3and Z 4represent 4 valency organic groups, R 18represent the alkyl that carbonatoms is 2～10, h represents 1～50 integer.
11. resin combinations as claimed in claim 10, is characterized in that, in the whole diamines in described polyimide precursor, the content of diamines with the structure of following general formula (5) be 15 % by mole above below 85 % by mole,
Figure FDA0000369142900000023
In formula (5), R 18represent the alkyl that carbonatoms is 2～10, h represents 1～50 integer.
12. resin combinations as claimed in claim 1, is characterized in that, in the diamines in described polyimide precursor, also comprise the aromatic diamine that at least one following general formula (6) represents,
Figure FDA0000369142900000031
In formula (6), R 19with following formula (7) or following general formula (8), represent,
Figure FDA0000369142900000032
In formula (8), R 20represent singly-bound ,-O-,-SO 2-or-C (CH 3) 2-.
13. resin combinations as claimed in claim 12, is characterized in that, described aromatic diamine is two (3-amino-benzene oxygen) benzene of 1,3-.
14. resin combinations as claimed in claim 1, is characterized in that, described in there is the resin that the compound of heat cross-linking functional group forms with monomer polymerization and there is flame retardant resistance.
15. resin combinations as claimed in claim 1, it is characterized in that, described in there is heat cross-linking functional group compound be at least one compound selecting in the group that free triazine based compound, benzoxazine based compound, epoxy based compound and blocked isocyanate based compound form.
16. resin combinations as claimed in claim 1, is characterized in that, described in there is heat cross-linking functional group compound be to there is the compound that does not need in fact the heat cross-linking of heat cross-linking promotor functional group.
17. resin combinations as claimed in claim 1, is characterized in that, with respect to polyimide precursor described in 100 mass parts, contain 1 mass parts～40 mass parts described in there is the compound of heat cross-linking functional group.
18. resin combinations as claimed in claim 1, is characterized in that, the imide rate of described polyimide precursor is more than 40% below 90%.
19. resin combinations as claimed in claim 1, is characterized in that, the acid number of described polyimide precursor is more than 16mgKOH/g.
20. resin combinations as claimed in claim 1, is characterized in that, described resin combination are preserved after 3 months to being changed to below 20% of viscosity.
21. resin combinations as claimed in claim 1, is characterized in that, the acid number of described polyimide precursor is that 16mgKOH/g is above to 70mgKOH/g, described resin combination are preserved after 1 month to being changed to below 10% of viscosity.
22. resin combinations as claimed in claim 1, it is characterized in that, the end of the main polymer chain of described polyimide precursor has carried out end-blocking with end-capping reagent, and described end-capping reagent is at least one derivative selecting in the group that free monoamine derivative or carboxylic acid derivative form.
23. resin combinations as claimed in claim 1, is characterized in that, the Young's modulus after thermofixation is 0.3GPa～1.4GPa, and in solder bath, when flooding 60 seconds for 260 ℃, nothing expands, burns.
24. resin combinations as claimed in claim 1, is characterized in that, it also contains fire retardant, and in described resin combination, halogen series elements content is below 1000ppm, has the flame retardant resistance of VTM-0 according to UL-94 standard.
25. 1 kinds of resin composition for screen printing, the resin combination described in its any one that is claim 1～claim 24, is characterized in that, its solid component concentration is more than 45%; By silk screen printing, on base material, print, dry after, dry film thickness is more than 15 μ m, and spreads and sinks in that to ooze be below 40 μ m.
The protective membrane formation material of 26. 1 kinds of tellites, is characterized in that, it consists of the resin combination described in any one of claim 1～claim 24.
27. 1 kinds of cured articles, is characterized in that, it is by obtaining the resin combination thermofixation described in any one of claim 1～claim 24.
28. 1 kinds of circuit substrates, is characterized in that, it possesses: have the cured article described in the surperficial claim 27 of base material described in the base material of wiring and coating.
29. 1 kinds of printed circuit board (PCB)s, is characterized in that, it obtains by comprising the method for following operation:
Right to use requires the resin composition for screen printing described in 25, has on the flexible printed circuit board of parts installation portion, utilizes the position of silk screen print method beyond parts are installed needed bonding part to print this resin combination.
CN201080024194.9A 2009-06-09 2010-06-09 Resin composition, cured product, and circuit board using same Expired - Fee Related CN102449070B (en)

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