CN103270070A - Resin composition, cured object, resin film, and wiring board - Google Patents

Resin composition, cured object, resin film, and wiring board Download PDF

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CN103270070A
CN103270070A CN2011800613170A CN201180061317A CN103270070A CN 103270070 A CN103270070 A CN 103270070A CN 2011800613170 A CN2011800613170 A CN 2011800613170A CN 201180061317 A CN201180061317 A CN 201180061317A CN 103270070 A CN103270070 A CN 103270070A
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compound
resin combination
polyimide
carbonatoms
general formula
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CN103270070B (en
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足立弘明
日下部透
佐佐木洋朗
山本正树
饭塚康史
水村华菜子
下田浩一朗
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Asahi Kasei Corp
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Asahi Chemical Co Ltd
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    • 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
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • 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
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    • 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
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    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Abstract

Provided is a resin composition with which cure warpage can be mitigated and which has excellent heat resistance and is suitable for use as a material for the surface-protective film or interlayer dielectric of a semiconductor element or for a protective dielectric, interlayer dielectric, or the like for printed wiring boards. Also provided are a resin film obtained using the resin composition and a wiring board obtained using the composition or film. This resin composition is characterized by comprising (A) a polymer, (B) a polyfunctional hydroxylated compound having two or more hydroxy groups, and (C) a polyfunctional crosslinking compound having two or more crosslinking functional groups which form crosslinks between the crosslinking compound and the polymer and/or polyfunctional hydroxylated compound, the polyfunctional crosslinking compound being capable of forming three-dimensional crosslinks between the crosslinking compound and the polymer and/or polyfunctional hydroxylated compound.

Description

Resin combination, cured article, resin molding and wiring board
Technical field
The present invention relates to surface protection film, interlayer dielectric, conductor package substrate, the bonding sheet as semiconductor element, the useful resin combination of material of use in printed circuit board protection insulating film; Used the cured article of resin combination; The wiring board that has used the resin molding of resin combination and used them.
Background technology
As the material of the surface protection film of semiconductor element, interlayer dielectric, use in printed circuit board protection insulating film, using the resin combination of the polyimide system of excellent heat resistance.Particularly, under the situation of resin combination as the insulating material of flexible printed circuit board with polyimide system, the warpage after also requiring to solidify except thermotolerance is few.As excellent heat resistance and the resin combination of the polyimide of the warpage after can reducing curing system, the polyimide that has proposed to be made of the terminal oligopolymer of ester and the terminal oligopolymer of amine is printing ink (for example, referring to patent documentation 1).
Polyimide about record in the patent documentation 1 is printing ink, after coating on the flexible wiring circuit, heat-treats and imidization with the temperature more than 250 ℃, uses then.In this imidization operation, because the caused stress of ring-closure reaction that desolventizing reaches and the imidization of oligopolymer accompanies, formed polyimide resin produces and shrinks.Therefore, the inhibition of warpage may not be abundant, and processibility also has problems.In addition, in circuit material, use under the situation of Copper Foil, also exist carboxyl and wiring material to react, cause the problem of wiring material oxidation because of the thermal treatment more than 250 ℃.
In addition, also can carry out the imidization under the low temperature, the polyimide precursor of warpage after curing can be reduced in exploitation.As such polyimide precursor, (for example can enumerate the polyimide precursor of the non-silicone-based of having used the alkyl oxide diamines, referring to patent documentation 2) and used the diamino siloxanes as polyimide precursor (for example, referring to patent documentation 3, patent documentation 4) of the silicone-based of two amine components etc.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 2-145664 communique
Patent documentation 2: TOHKEMY 2006-321924 communique
Patent documentation 3: Japanese kokai publication sho 57-143328 communique
Patent documentation 4: Japanese kokai publication sho 58-13631 communique
Summary of the invention
The problem that invention will solve
But, in the patent documentation 2 polyimide precursor of record have from the polyamic acid structure of alkyl oxide diamines and from the polyimide structures of aromatic diamine as structural unit.Therefore, under the situation of resin combination for the insulating material of flexible printed circuit board as polyimide system, there are the polyimide position contraction from aromatic diamine, the problem of the warpage in the time of may not fully suppressing to solidify.
In addition; the polyimide precursor of record is the polyimide precursor of silicone-based in patent documentation 3 and the patent documentation 4; thereby coating circuit substrate as the resin combination of polyimide system and making its imidization and form under the situation of protective membrane of circuit; in prepreg and bonding operation thereafter, have the silicone position becomes low surface tension and high water-repellancy, repels bonding composition on the surface of surface segregation, protective membrane situation sometimes.Therefore, there is the problem that may not necessarily access sufficient performance as protective membrane in the bonding force deficiency between protective membrane and the adhesive sheet.
The present invention carries out in view of this point, and its purpose is to provide warpage, the excellent heat resistance that can reduce when solidifying, the resin combination that can suit to protect as surface protection film, interlayer dielectric, the use in printed circuit board of semiconductor element the material of insulating film, interlayer dielectric etc. simultaneously; Used the resin molding of resin combination; With the wiring board that has used them.
For the scheme of dealing with problems
Resin combination of the present invention is characterised in that it contains: (A) macromolecular compound; (B) has the multifunctional hydroxy-containing compounds of 2 above hydroxyls; (C) have and above-mentioned macromolecular compound and/or above-mentioned multifunctional hydroxy-containing compounds between form the multifunctional cross-linked compound of the bridging property functional group more than 2 of cross-link bond, above-mentioned multifunctional cross-linked compound can and above-mentioned macromolecular compound and/or above-mentioned multifunctional hydroxy-containing compounds between form three-dimensional cross-linked.
In the resin combination of the present invention, preferably, above-mentioned macromolecular compound has imide and/or amide group, above-mentioned three-dimensional cross-linked C=O base and/or the NH base of comprising.
In the resin combination of the present invention, preferred above-mentioned multifunctional hydroxy-containing compounds and/or above-mentioned multifunctional cross-linked compound are more than 3 official's energy.
In the resin combination of the present invention, preferred above-mentioned macromolecular compound has hydroxyl and/or carboxyl.
In the resin combination of the present invention, as above-mentioned multifunctional hydroxy-containing compounds, preferably comprise and be selected from least a in two terminal phenol-modified silicone, polybutadiene polyol, hydrogenated butadiene polymer polyvalent alcohol and the polycarbonate polyol.
In the resin combination of the present invention, preferred above-mentioned multifunctional hydroxy-containing compounds has aliphatic structure.
In the resin combination of the present invention, preferred above-mentioned multifunctional hydroxy-containing compounds is polycarbonate polyol.
In the resin combination of the present invention, as above-mentioned multifunctional cross-linked compound, preferably comprise the polyfunctional isocyanate's compound with 2 above isocyanate group.
In the resin combination of the present invention, preferred above-mentioned multifunctional cross-linked compound comprises the blocked isocyanate base more than 2.
In the resin combination of the present invention, the mol ratio of the bridging property functional group that the hydroxyl that preferred above-mentioned multifunctional hydroxy-containing compounds contains and above-mentioned multifunctional cross-linked compound contain is hydroxyl/bridging property functional group=0.5～1.
In the resin combination of the present invention, with respect to above-mentioned macromolecular compound 100 mass parts, the content of preferred above-mentioned multifunctional hydroxy-containing compounds is 5 mass parts～60 mass parts.
In the resin combination of the present invention, with respect to above-mentioned macromolecular compound 100 mass parts, the content of preferred above-mentioned multifunctional cross-linked compound is 5 mass parts～60 mass parts.
In the resin combination of the present invention, the number-average molecular weight of preferred above-mentioned multifunctional hydroxy-containing compounds is 500～3000.
In the resin combination of the present invention, preferred above-mentioned macromolecular compound has the repeating structure of following general formula (1) expression.
General formula (1)
Figure BDA00003375991600031
(in the formula (1), Y 1The organic group of expression divalent, Z 1The organic group of representing 4 valencys.A represents 1～50 integer.)
In the resin combination of the present invention, preferred above-mentioned macromolecular compound is polyimide.
In the resin combination of the present invention, preferred above-mentioned macromolecular compound has the repeating structure of following general formula (2) expression.
General formula (2)
Figure BDA00003375991600041
(in the formula (2), Z 1And Z 2The organic group of representing 4 valencys, Y 1, Y 2, Y 3, Y 4And Y 5Represent that independently of one another carbonatoms is that 1～carbonatoms is 5 alkylidene group, can have side chain.B, c and d represent 1～50 integer independently of one another.)
In the resin combination of the present invention, preferred above-mentioned macromolecular compound has the polyamic acid structure of the polyimide structures of following general formula (3) expression and following general formula (4) expression respectively as repeated structural unit.
General formula (3)
General formula (4)
Figure BDA00003375991600043
(in formula (3) and the formula (4), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency.R 3, R 6, R 9, R 12And R 15Represent that independently of one another carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, m, n, p represent the integer below 100 more than 0 independently of one another.R 16The organic group of representing 4 valencys, R 17The expression carbonatoms is that 1～carbonatoms is the organic group of 90 divalent.)
In the resin combination of the present invention, as two amine components of the polyimide that constitutes above-mentioned general formula (3) expression, preferably comprise the diamines of following general formula (5) expression.
General formula (5)
Figure BDA00003375991600044
(in the formula (5), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency.R 3, R 6, R 9, R 12And R 15Represent that independently of one another carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, m, n, p represent the integer below 30 more than 0 independently of one another, satisfy 1 ≦ (m+n+p) ≦ 30.)
In the resin combination of the present invention, preferred above-mentioned macromolecular compound has the structure of following general formula (6) expression as repeating unit.
General formula (6)
(in the formula (6), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency.R 3, R 6, R 9, R 12And R 15The expression carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, and m, n, p represent the integer below 30 more than 0 independently of one another.R 16The organic group of representing 4 valencys, R 17The expression carbonatoms is that 1～carbonatoms is the organic group of 90 divalent.A, B, C represent the mole % of each unit, satisfy 0.10 ≦ (A+B)/(A+B+C) ≦ 0.85.)
In the resin combination of the present invention, preferred above-mentioned macromolecular compound has the polyamic acid structure of the polyimide structures of following general formula (7) expression and following general formula (8) expression as structural unit.
General formula (7)
General formula (8)
Figure BDA00003375991600053
(in formula (7) and the formula (8), Z 3And Z 4Be the organic group from the tetracarboxylic dianhydride's of following general formula (9) expression 4 valencys, can be identical separately also can be different.R 18The expression carbonatoms is that 1～carbonatoms is the organic group of 30 divalent, R 19The expression carbonatoms is that 1～carbonatoms is the organic group of 30 1 valency, and e represents the integer below 20 more than 1.)
General formula (9)
Figure BDA00003375991600054
In the resin combination of the present invention, preferably contain: (D) have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound and (E) Photoepolymerizationinitiater initiater.
In the resin combination of the present invention, as above-mentioned have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound, preferably comprise (methyl) acrylic compound with two keys more than 3.
In the resin combination of the present invention, as above-mentioned (methyl) acrylic compound with two keys more than 3, preferably comprise the compound of following general formula (10) expression.
General formula (10)
Figure BDA00003375991600061
(in the formula (10), R 20Expression hydrogen atom or methyl, a plurality of E represent that independently of one another carbonatoms is that 2～carbonatoms is 5 alkylidene group, can be identical separately also can be different.F is 1～10 integer.)
In the resin combination of the present invention, as above-mentioned have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound, preferably comprise (methyl) acrylic compound with 2 two keys and have (methyl) acrylic compound of two keys more than 3.
In the resin combination of the present invention, preferably contain (F) phosphorus compound.
In the resin combination of the present invention, as above-mentioned phosphorus compound, preferred package phosphoric acid ester cpds and/or phosphazene compound.
Resin combination of the present invention is characterised in that, in 85 ℃ of temperature, humidity 85%, 1000 hours insulating reliability test, layer insulation resistance is 10 9More than the Ω, 120 ℃～220 ℃ viscosity is 5000PaS～100000PaS, and it is plasticity part more than 50% less than 20% elastic part and elongation that this resin combination has elongation, and the thickness of interlayer insulating film is below the 40 μ m.
Cured article of the present invention is characterised in that it is by obtaining above-mentioned resin combination in 15 minutes～60 minutes 160 ℃～200 ℃ heating after 5 minutes～60 minutes 100 ℃～130 ℃ heating again.
Resin molding of the present invention is characterised in that it possesses base material and the above-mentioned resin combination that is arranged on the above-mentioned base material.
In the resin molding of the present invention, preferred above-mentioned base material is carrier film.
In the resin molding of the present invention, preferably it possesses the mulch film that is arranged on the above-mentioned resin combination.
In the resin molding of the present invention, preferred above-mentioned base material is Copper Foil.
Wiring board of the present invention is characterised in that it possesses: have the base material of distribution and the above-mentioned resin combination that arranges in the mode that covers above-mentioned distribution.
The effect of invention
According to the present invention, can provide warpage, the excellent heat resistance that can reduce when solidifying, the resin combination that can suit to protect as surface protection film, interlayer dielectric, the use in printed circuit board of semiconductor element the material of insulating film, interlayer dielectric etc. simultaneously; Used the resin molding of resin combination; With the wiring board that has used them.
Description of drawings
Fig. 1 is the figure of summary of manufacturing process that the layer flexible wiring board of present embodiment is shown.
Embodiment
In recent years, be accompanied by multifunction and the lightweight of electronicss such as mobile telephone, the multifunction that is used for the slimming of flexible printed board of various electronicss and parts installation etc. advances.In the manufacturing process of flexible printed board; having used epoxy is that resin and polyimide are resin; but with the resin of epoxy system as under the situation of protective membrane, may not fully obtain necessary high insulating reliability and flexibility, low bounce, flame retardant resistance in the slimming of flexible printed board.In addition, epoxy is that resin has reactivity, thereby the storage stability shortcoming.In addition, even be under the situation of resin having used existing polyimide, reduction and the stable on heating polyimide that can realize warpage are the resin costliness, the reduction of the warpage of the cured article that expectation is simultaneously accompanied with imidization and the good resin combination of thermotolerance.
The inventor be conceived to can and macromolecular compound and/or multifunctional hydroxy-containing compounds between form three-dimensional cross-linked multifunctional cross-linked compound.And, the inventor considers by the resin combination that comprises macromolecular compound and/or multifunctional hydroxy-containing compounds and multifunctional cross-linked compound is heated, thereby utilizes form three-dimensional cross-linked and the formation three-dimensional network between multifunctional cross-linked compound and multifunctional hydroxy-containing compounds.In addition, the inventor finds, by this three-dimensional network, can reduce the warpage when solidifying, and can realize having excellent stable on heating resin combination, has finished the present invention thus.
That is, resin combination of the present invention contains: (A) macromolecular compound; (B) has the multifunctional hydroxy-containing compounds of 2 above hydroxyls; (C) have and macromolecular compound and/or multifunctional hydroxy-containing compounds between form the multifunctional cross-linked compound of the bridging property functional group more than 2 of cross-link bond, multifunctional cross-linked compound can and macromolecular compound and/or multifunctional hydroxy-containing compounds between form three-dimensional cross-linked.
In this resin combination, three-dimensional cross-linked by heating formation between the hydroxyl of the bridging property functional group of multifunctional cross-linked compound and multifunctional hydroxy-containing compounds, by this three-dimensional cross-linked formation three-dimensional network.Thus, the contraction of the macromolecular compound in the time of can suppressing resin combination curing, the consistency between macromolecular compound, multifunctional hydroxy-containing compounds and multifunctional cross-linked compound is improved simultaneously.Its result; the resin combination that can be achieved as follows; it can reduce the warpage when solidifying, excellent heat resistance, the material of can suit simultaneously to protect as surface protection film, interlayer dielectric, the use in printed circuit board of semiconductor element insulating film, interlayer dielectric etc.
In the resin combination of the present invention, preferably, macromolecular compound has imide and/or amide group, the three-dimensional cross-linked C=O of the comprising base and/or the NH base that form between multifunctional hydroxy-containing compounds and multifunctional cross-linked compound.By this formation, generation is based on the interaction of hydrogen bond between the imide of the three-dimensional cross-linked C=O base that contains and/or NH base and macromolecular compound and/or amide group, so the consistency between macromolecular compound, multifunctional hydroxy-containing compounds and multifunctional cross-linked compound further improves.Thus, can further reduce the warpage when solidifying, further improve thermotolerance.
In the resin combination of the present invention, as macromolecular compound, multifunctional hydroxy-containing compounds and multifunctional cross-linked compound, as long as can between macromolecular compound and/or multifunctional hydroxy-containing compounds and multifunctional cross-linked compound, form three-dimensional cross-linkedly by heating grade, then can in playing the scope of effect of the present invention, be used in combination all cpds.Below, the mode of resin combination of the present invention is elaborated.
(the 1st mode)
About the resin combination of the 1st mode of the present invention, multifunctional hydroxy-containing compounds and/or multifunctional cross-linked compound are more than 3 official's energy.Like this, if at least one of multifunctional hydroxy-containing compounds or multifunctional cross-linked compound is more than 3 official's energy, the hydroxyl more than 2 that then can be by multifunctional hydroxy-containing compounds and the bridging property functional group more than 2 of multifunctional cross-linked compound are (for example, isocyanate group, oxazolinyl) the C=O base that the crosslinking reaction between and forming comprises more than 2 and/or NH base three-dimensional cross-linked forms three-dimensional network.In this case, utilize not to be situated between by the three-dimensional network between the formed multifunctional hydroxy-containing compounds of macromolecular compound and the multifunctional cross-linked compound, can suppress the contraction of macromolecular compound, show abundant reduction and the excellent thermotolerance of warpage.
In the resin combination of the 1st mode of the present invention, the three-dimensional network that utilization forms between multifunctional hydroxy-containing compounds and multifunctional cross-linked compound, the contraction of macromolecular compound can be suppressed, therefore effect of the present invention can be under the situation of the molecular structure that is not restricted to macromolecular compound, played.Therefore, for example, even under the situation of using the macromolecular compound cheaply do not have complicated molecular structure, the warpage in the time of also can reducing the curing of resin combination shows excellent thermotolerance.
(the 2nd mode)
In the resin combination of the 2nd mode of the present invention, macromolecular compound has hydroxyl and/or carboxyl.Like this, macromolecular compound has any one in hydroxyl and the carboxyl, also forms cross-link bond thus between the bridging property functional group (for example, isocyanate group, oxazolinyl) of hydroxyl and/or carboxyl and the multifunctional cross-linked compound of macromolecular compound.Thus, between macromolecular compound, multifunctional hydroxy-containing compounds and multifunctional cross-linked compound, form the three-dimensional network that is situated between by macromolecular compound, therefore can improve the consistency of macromolecular compound, multifunctional hydroxy-containing compounds and multifunctional cross-linked compound, further suppress the contraction of macromolecular compound, warpage in the time of can reducing the curing of resin combination especially shows excellent thermotolerance.
In the resin combination of the 2nd mode of the present invention, be situated between that it is three-dimensional cross-linked to be formed by macromolecular compound, even therefore at least one of multifunctional hydroxy-containing compounds and multifunctional cross-linked compound is not more than 3 official's energy, also can form three-dimensional network.In addition, be situated between by the three-dimensional network of macromolecular compound owing to formed, so the consistency of macromolecular compound and multifunctional hydroxy-containing compounds and multifunctional cross-linked compound is further enhanced.Therefore, even under situation about using with the low macromolecular compound of the consistency of multifunctional hydroxy-containing compounds and multifunctional cross-linked compound, also can access the resin combination of the practicality in the manufacturing process that can be used for flexible printed circuit board etc.Below, each constitutive requirements is elaborated.
(A) macromolecular compound
As macromolecular compound, can in playing the scope of effect of the present invention, use various macromolecular compounds.As macromolecular compound, for example, can enumerate polymeric amide, polyamidoimide, polyamic acid, polyamic acid by polyimide of imidization etc.Need to prove, among the present invention, the part that polyimide comprises polyamic acid by the polyimide precursor of imidization and all polyamic acids by the polyimide of imidization.
In the resin combination of the 1st mode, as macromolecular compound, to molecular structure without limits, can use above-mentioned various macromolecular compounds such as polyimide.Among these, as macromolecular compound, from thermotolerance and anti-hygroscopic aspect, preferably use polyimide.
In the resin combination of the 2nd mode, as macromolecular compound, use the macromolecular compound that has hydroxyl and/or carboxyl in the molecular chain.As such macromolecular compound, can use polyimide that has hydroxyl or carboxyl in polyamic acid and the molecular chain etc.
Polyimide obtains by making dicarboxylic anhydride and diamine reactant.Using under the situation of polyimide as macromolecular compound, for example, can use mainly to have polyimide structures as the polyimide of repeated structural unit, also can use to have polyimide structures and polyamic acid structure as the polyimide of repeated structural unit.
As macromolecular compound, for example, can use the macromolecular compound of the repeated structural unit with following general formula (1) expression.
General formula (1)
Figure BDA00003375991600101
(in the formula (1), Y 1The organic group of expression divalent, Z 1The organic group of representing 4 valencys.A represents 1～50 integer.)
In addition, as macromolecular compound, can use the reaction of alkyl oxide diamines and dicarboxylic anhydride and the polyimide of the non-silicone-based that obtains, also can use diamino siloxanes and dicarboxylic anhydride to react and the polyimide of the silicone-based that obtains.
As macromolecular compound, the preferred macromolecular compound that uses the repeating structure with following general formula (2) expression.In this macromolecular compound, owing to have the oxyalkylene alkyl, thereby molecular chain is endowed flexibility, and the solvent soluble of macromolecular compound is improved.
General formula (2)
Figure BDA00003375991600102
(in the formula (2), Z 1And Z 2The organic group of representing 4 valencys, Y 1, Y 2, Y 3, Y 4And Y 5Represent that independently of one another carbonatoms is that 1～carbonatoms is 5 alkylidene group, can have side chain.B, c and d represent 1～50 integer independently of one another.)
In addition, as macromolecular compound, preferred use has the polyamic acid structure of the polyimide structures of following general formula (3) expression and following general formula (4) expression respectively as the macromolecular compound of repeated structural unit.In this macromolecular compound, in polyimide structures, contain the alkyl oxide structure, contain the polyamic acid structure simultaneously, thereby can give the molecular chain flexibility and do not damage molecular weight stability, so stable developing is improved.In addition, in this macromolecular compound, the carboxyl of the polyamic acid structure that following general formula (4) contains and the bridging property functional group of multifunctional cross-linked compound are (for example, isocyanate group, oxazolinyl etc.) reaction, therefore between macromolecular compound and multifunctional cross-linked compound, also form crosslinked, the contraction of the polyimide in the time of can further suppressing to solidify.In addition, carboxyl and bridging property functional group reactions make the carboxyl in the cured article reduce thus, thereby can access the cured article of insulativity excellence.
General formula (3)
Figure BDA00003375991600111
General formula (4)
Figure BDA00003375991600112
(in formula (3) and the formula (4), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency.R 3, R 6, R 9, R 12And R 15Represent that independently of one another carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, m, n, p represent the integer below 100 more than 0 independently of one another.R 16The organic group of representing 4 valencys, R 17The expression carbonatoms is that 1～carbonatoms is the organic group of 90 divalent.)
In addition, as macromolecular compound, preferably comprise the diamines of following general formula (5) expression as two amine components of the macromolecular compound that constitutes above-mentioned general formula (3) expression.
General formula (5)
Figure BDA00003375991600113
(in the formula (5), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency.R 3, R 6, R 9, R 12And R 15Represent that independently of one another carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, m, n, p represent the integer below 30 more than 0 independently of one another, satisfy 1 ≦ (m+n+p) ≦ 30.)
In addition, as macromolecular compound, preferred use has the structure of following general formula (6) expression as the macromolecular compound of repeating unit.
General formula (6)
Figure BDA00003375991600114
(in the formula (6), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency.R 3, R 6, R 9, R 12And R 15The expression carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, and m, n, p represent the integer below 30 more than 0 independently of one another.R 16The organic group of representing 4 valencys, R 17The expression carbonatoms is that 1～carbonatoms is the organic group of 90 divalent.A, B, C represent the mole % of each unit, satisfy 0.10 ≦ (A+B)/(A+B+C) ≦ 0.85.)
In the macromolecular compound of above-mentioned general formula (6) expression, by satisfying 0.10 ≦ (A+B)/(A+B+C), the alkyl oxide structure in the molecular chain increases, and the flexibility of the molecular chain of macromolecular compound improves, so can reduce the warpage after the curing.In addition, by satisfying (A+B)/(A+B+C) ≦ 0.85, the carboxyl in the molecular chain increases, and therefore shows the solvability of cured article in alkaline-based developer, and development property becomes good simultaneously.
In addition, as macromolecular compound, the preferred polyamic acid structure of polyimide structures with following general formula (7) expression and following general formula (8) expression of using is as the macromolecular compound of repeated structural unit.In this macromolecular compound, comprise the siloxanes position in the polyimide structures, thereby give the flexibility of polyimide structures appropriateness, therefore can suppress the contraction of the molecular chain of macromolecular compound, the warpage after can suppressing to solidify.In addition, owing to comprise aromatic nucleus in the polyamic acid structure, thereby can suppress the reduction of the molecular weight of polyamic acid structure, the development time stability of the storage stability of resin combination and the dry film that obtained by resin combination is improved.In addition, polyimide structures and polyamic acid structure comprise the organic group from tetracarboxylic dianhydride's 4 valencys, therefore give the rigidity of molecular chain appropriateness, and thermotolerance improves, and insulating reliability improves.
General formula (7)
Figure BDA00003375991600121
General formula (8)
Figure BDA00003375991600122
(in formula (7) and the formula (8), Z 3And Z 4Be the organic group from the tetracarboxylic dianhydride's of following general formula (9) expression 4 valencys, can be identical separately also can be different.R 18The expression carbonatoms is that 1～carbonatoms is the organic group of 30 divalent, R 19The expression carbonatoms is that 1～carbonatoms is the organic group of 30 1 valency, and e represents the integer below 20 more than 1.)
General formula (9)
Figure BDA00003375991600131
In addition, as macromolecular compound, have in use under the situation of polyamic acid structure as the macromolecular compound of repeated structural unit of the polyimide structures of above-mentioned general formula (7) expression and above-mentioned general formula (8) expression, the bridging property functional group of the carboxyl that the polyamic acid structure contains and multifunctional cross-linked compound (for example, isocyanate group) reaction.Thus, macromolecular compound enters the three-dimensional network between multifunctional hydroxy-containing compounds and the multifunctional cross-linked compound, can suppress the cured article at silicone position in the segregation on surface.Therefore thus, can suppress the performance of capillary reduction and water-repellancy, even also can obtain good bonding force making under the situation of protective membrane.
(B) multifunctional hydroxy-containing compounds
As multifunctional hydroxy-containing compounds, in the resin combination of the 1st mode and the 2nd mode, can use common multifunctional hydroxy-containing compounds.As multifunctional hydroxy-containing compounds, need only the hydroxyl that has in the molecular chain more than 2, then can in playing the scope of effect of the present invention, use various hydroxy-containing compounds.As multifunctional hydroxy-containing compounds, for example, can use the various glycol as the 2 officials energy hydroxy-containing compounds that contains 2 hydroxyls, also can use the various polyvalent alcohols that contain 3 above hydroxyls.Among these, from at multifunctional hydroxy-containing compounds and multifunctional cross-linked compound (for example, polyfunctional isocyanate, Duo Guan Neng oxazoline compound) between form the cross-link bond more than 2 the aspect consider, as multifunctional hydroxy-containing compounds, the preferred multifunctional hydroxy-containing compounds that contains 2 above hydroxyls that uses.
As multifunctional hydroxy-containing compounds, consider from the aspect that improves insulativity, preferably comprise and be selected from least a in two terminal phenol-modified silicone, polybutadiene polyol, hydrogenated butadiene polymer polyvalent alcohol and the polycarbonate polyol.In addition, as multifunctional hydroxy-containing compounds, preferably has aliphatic structure.Thus, when water tolerance improves, become low elasticity, therefore can improve warpage and insulating reliability.From the above considerations, as multifunctional hydroxy-containing compounds, among the above-mentioned concrete example of enumerating, preferred hydrogenated butadiene polymer polyvalent alcohol, polycarbonate polyol are particularly considered from the aspect that can reduce warpage, preferably use polycarbonate polyol.
In the resin combination of the present invention, with respect to polyimide 100 mass parts, the content of multifunctional hydroxy-containing compounds is preferably 5 mass parts～60 mass parts.Be more than 5 mass parts by making multifunctional hydroxy-containing compounds, can and multifunctional cross-linked compound between form crosslinkedly fully, therefore can reduce the warpage when solidifying.In addition, be below 60 mass parts by making multifunctional hydroxy-containing compounds, the excessive hydroxyl in the resin combination reduces, so the insulating reliability after the curing of resin combination improves.In addition, with respect to polyimide 100 mass parts, the content of multifunctional hydroxy-containing compounds is preferably 5 mass parts～30 mass parts.
As multifunctional hydroxy-containing compounds, preferably using number-average molecular weight is 500～3000 material.Herein, number-average molecular weight refers to the number-average molecular weight by the vinylbenzene conversion molecular weight of gel permeation chromatography.If the number-average molecular weight of multifunctional hydroxy-containing compounds is that then resin combination becomes low elasticity more than 500, therefore can reduce warpage.In addition, if the number-average molecular weight of multifunctional hydroxy-containing compounds is below 3000, then can reduce the viscosity of resin combination, therefore become good at the wiring part of wiring board and the imbedibility of through-hole section.In addition, as the number-average molecular weight of multifunctional hydroxy-containing compounds, the aspect from the reduction of the low elasticity of resin combination and viscosity is preferably 500～2000.
(C) multifunctional cross-linked compound
As multifunctional cross-linked compound, in the resin combination of the 1st mode and the 2nd mode, can use common multifunctional cross-linked compound.As multifunctional cross-linked compound, as long as have bridging property functional group more than 2, then can in playing the scope of effect of the present invention, use various multifunctional cross-linked compounds.Herein, bridging property functional group refer to can and the hydroxyl of the hydroxyl of macromolecular compound or carboxyl and multifunctional hydroxy-containing compounds between form the functional group of cross-link bond.As bridging property functional group, for example, can enumerate isocyanate group, oxazolinyl etc., but be not limited to these.In addition, as multifunctional cross-linked compound, can use 2 officials with 2 bridging property functional groups can cross-linked compound, also can use the cross-linked compound with 3 above bridging property functional groups.As multifunctional cross-linked compound, for example, can enumerate the polyfunctional isocyanate's compound with 2 above isocyanate group and have Duo Guan Neng oxazoline compound of 2 Yi Shang oxazolinyls etc.
As multifunctional cross-linked compound, the preferred polyfunctional isocyanate's compound that contains 2 above isocyanate group that uses.By this structure, being situated between between the hydroxyl of the isocyanate group of polyfunctional isocyanate's compound and multifunctional hydroxy-containing compounds forms three-dimensional network by amino-formate bond, simultaneously between imide that macromolecular compound contains and amide group or hydroxyl and carboxyl and the contained C=O base that has of carboxylamine ester structure and NH base by hydrogen bond generation interaction.Thus, can improve the low bounce of resin combination, simultaneously by the plasticity of macromolecular compound and elastic compoundization of resin combination, make resin combination show the flowability of appropriateness.Its result can take into account for example needed opposite two kinds of rerum naturas (flowability and viscosity) when resin combination being used as the interlayer dielectric of multi-layer flexible printed circuit board, therefore can guarantee excellent performance as interlayer dielectric.As polyfunctional isocyanate's compound, as long as have isocyanate group more than 2, then can in playing the scope of effect of the present invention, use various isocyanate compounds.
In addition, under with the situation of resin combination of the present invention as the interlayer dielectric of layer flexible wiring board etc., require on the one hand resin combination to flow into wiring part and the through-hole section of wiring board, require resin combination not flow out from the end of wiring board on the other hand and to keep to a certain degree.This be because, if flow into to through hole fully in the suppression process under the high pressure, resin combination flows out from the end of wiring board usually, the thickness attenuation of the insulation layer of the end of wiring board, insulativity might reduce.Therefore, for example, among above-mentioned resin combination, using under the situation of polyfunctional isocyanate's compound as multifunctional cross-linked compound, multifunctional hydroxy-containing compounds and polyfunctional isocyanate's compound are by the amino-formate bond that forms between the hydroxyl of the isocyanate group of polyfunctional isocyanate's compound and multifunctional hydroxy-containing compounds and bonding produces interaction by the hydrogen bond between carboxylamine ester structure and the macromolecular compound simultaneously.Thus, utilize the plasticity of macromolecular compound and elastic compoundization of resin combination, can take into account opposite, resin combination and flow into needed flowability and in order to ensure the thickness of the insulating film of the end of wiring part and prevent that resin combination from flowing out the viscosity of needed appropriateness to wiring part.Its result has prevented that resin combination from flowing out from the end of wiring board, and resin combination does not flow out from the end of wiring board and to keep to a certain degree, therefore can realize very good imbedibility.
In addition, as multifunctional cross-linked compound, can also use the polyfunctional isocyanate's compound and the resulting blocked isocyanate that contains the blocked isocyanate base of end-capping reagent reaction that contain 2 above isocyanate group.Under this situation, as multifunctional cross-linked compound, the high molecular that produces from the reaction with the hydroxyl of multifunctional hydroxy-containing compounds, be cross-linked to form that the thermotolerance that produces improves and the aspect of chemical proofing, preferably contain the blocked isocyanate base more than 2.In addition, consider from the aspect that forms the cross-link bond between multifunctional hydroxy-containing compounds and the isocyanate compound, as multifunctional hydroxy-containing compounds, preferred polyfunctional isocyanate's compound or the blocked isocyanate that contains 2 above isocyanate group that use.
In addition, as multifunctional cross-linked compound, also preferred use has the Duo Guan Neng oxazoline compound of 2 Yi Shang oxazolinyls.By this structure, Duo Guan Neng oxazoline compound De oxazolinyl and the hydroxyl of multifunctional hydroxy-containing compounds between reaction and form amido linkage.In addition, macromolecular compound has under the situation of hydroxyl, carboxyl, Duo Guan Neng oxazoline compound De oxazolinyl and hydroxyl, carboxyl between reaction and form amido linkage and/or comprise the crosslinking structure (three-dimensional cross-linked) of carboxylic acid amide esters.Thus, between macromolecular compound, multifunctional hydroxy-containing compounds and multifunctional cross-linked compound, form amido linkage and/or based on the three-dimensional cross-linked three-dimensional network that comprises carboxylic acid amide esters, therefore by interaction and chemical bondings such as hydrogen bond between crosslinking structure and the macromolecular compound, the flexibility of multifunctional hydroxy-containing compounds macromolecular compound can be reflected to effectively, reduction and the excellent thermotolerance of sufficient warpage can be realized.As Duo Guan Neng oxazoline compound, as long as have 2 Yi Shang De oxazolinyls, then can in playing the scope of effect of the present invention, use Ge Zhong oxazoline compound.
In the resin combination of the present invention, with respect to macromolecular compound 100 mass parts, the content of multifunctional cross-linked compound is preferably 5 mass parts～60 mass parts.If the content of multifunctional cross-linked compound is more than 5 mass parts, then can and multifunctional hydroxy-containing compounds between form crosslinkedly fully, therefore can reduce the warpage when solidifying.In addition, if the content of multifunctional cross-linked compound is below 60 mass parts, then macromolecular compound flowability when heating and pressurizing becomes well, so the through hole imbedibility can improve.In addition, as the content of multifunctional cross-linked compound, with respect to macromolecular compound 100 mass parts, be preferably 5 mass parts～30 mass parts.
In the resin combination of the present invention, the mol ratio of the bridging property functional group that the hydroxyl that multifunctional hydroxy-containing compounds contains and multifunctional cross-linked compound contain is preferably hydroxyl/bridging property functional group=0.5～1.Thus, the hydroxyl that multifunctional hydroxy-containing compounds contains is excessive with respect to the bridging property functional group of multifunctional cross-linked compound, thereby the cross-link bond between multifunctional hydroxy-containing compounds and the multifunctional cross-linked compound moderately forms.Therefore, can suppress the contraction of the polyimide that accompanies with the curing of resin combination, the reduction of the sufficient warpage in the time of can realizing solidifying and excellent thermotolerance.
(D) sensitizer
Resin combination of the present invention is by containing sensitizer, thereby can be used as photosensitive polymer combination.As sensitizer, in the resin combination of the 1st mode and the 2nd mode, can use common sensitizer.As sensitizer, so long as have the compound that makes the character of structural changes and the variation of the solvability in solvent by rayed, then be not particularly limited, can use all cpds.As sensitizer, for example, can suit to use to have more than 2 (methyl) acrylic compound that can photopolymerisable unsaturated double-bond etc.
In addition, in the resin combination of the present invention, consider from the aspect that improves resolving power and insulativity, as have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound, preferably comprise (methyl) acrylic compound with two keys more than 3.
In addition, in the resin combination of the present invention, consider from the aspect that reduces insulating resistance value and warpage that (methyl) acrylic compound with two keys more than 3 is preferably the compound of following general formula (10) expression.The compound of following general formula (10) expression does not enter the skeleton of macromolecular compound and forms crosslinked body as second composition, and the contraction of macromolecular compound can suppress warpage in the time of therefore can preventing from solidifying.And by inference, because the compound of following general formula (10) expression does not have the functional group of reduction electrical insulating properties such as hydroxyl, thereby forms upright and outspoken crosslinked body, the second-order transition temperature of cured film (Tg) and Young's modulus raise, and insulating resistance value improves.
General formula (10)
Figure BDA00003375991600171
(in the formula (10), in the formula (10), R 20Expression hydrogen atom or methyl, a plurality of E represent that independently of one another carbonatoms is that 2～carbonatoms is 5 alkylidene group, can be identical separately also can be different.F is 1～10 integer.)
In the resin combination of the present invention, aspect from development and insulating reliability, as have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound, preferably comprise (methyl) acrylic compound with 2 two keys and have (methyl) acrylic compound of two keys more than 3.By inference, (methyl) acrylic compound that has more than 3 two keys and multifunctional hydroxy-containing compounds between form upright and outspoken crosslinked body, so the Young's modulus of cured film and second-order transition temperature (Tg) raise, insulating reliability improves.
(E) Photoepolymerizationinitiater initiater
In the resin combination of the present invention, state in the use under the situation of sensitizer, preferably be used in combination with Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, in the resin combination of the 1st mode and the 2nd mode, can use common Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, so long as activated the also compound of initiated polymerization by various active rays, ultraviolet ray etc., then can use all cpds.As Photoepolymerizationinitiater initiater, for example, can suit to use oxime ester class etc.
In the resin combination of the present invention, preferably contain have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound and Photoepolymerizationinitiater initiater.Thus, can suit as photosensitive polymer combination.
(F) fire retardant
In the resin combination of the present invention, preferably contain fire retardant.As fire retardant, in the resin combination of the 1st mode and the 2nd mode, can use common fire retardant.Kind as fire retardant is not particularly limited, and can enumerate halide, nitrogenous compound, P contained compound and inorganic combustion inhibitor etc.In addition, as phosphorus compound, then be not particularly limited so long as comprise the compound of phosphorus atom in the structure.As phosphorus compound, for example, can enumerate phosphate compound, phosphazene compound etc.These fire retardants can use a kind of, also can be use mixing two or more.Addition to fire retardant is not particularly limited, can the suitable change according to the kind of employed fire retardant.
In the resin combination of the present invention, the preferred package P contained compound.Thus, the flame retardant resistance of resin combination improves.
In addition, in the resin combination of the present invention, as phosphorus compound, preferred package phosphoric acid ester cpds and/or phosphazene compound.Thus, particularly the flame retardant resistance of resin combination improves.
In the resin combination of the present invention, by with preset temperature heating or dry, can access cured article (cured film).For this cured article, for example can be also dry by resin combination of the present invention being coated on the base material, thus use with the form of resin molding.In addition, the photosensitive polymer combination that contains sensitizer also can be used as photosensitive film and uses.These resin moldings and photosensitive film for example can suit as interlayer dielectric and the distribution protective membrane of flexible printed board.
Cured article of the present invention is by, after 5 minutes～60 minutes obtaining above-mentioned resin combination 100 ℃～130 ℃ heating 160 ℃～200 ℃ heating 15 minutes～60 minutes.
Resin molding of the present invention possesses base material and the resin combination that is arranged on this base material.Under this situation, as base material, can use Copper Foil and carrier film etc.In addition, in the resin molding of the present invention, preferably possess carrier film, be arranged at the resin combination on this carrier film and be arranged at mulch film on this resin combination.Thus, surface that can the nurse tree adipose membrane.
In the resin molding of the present invention, can use Copper Foil as base material, and at this Copper Foil above-mentioned resin combination is set.Like this, by resin combination and dry is set at Copper Foil, can suit as the interlayer dielectric of layer flexible wiring board etc.
Wiring board of the present invention possesses the base material with distribution and the above-mentioned resin combination that arranges in the mode that covers above-mentioned distribution.Like this, by in the mode that covers distribution resin combination being set, can suit as the protective membrane of the Wiring pattern of wiring board.
In the resin combination of the present invention, owing to comprise low-molecular-weight multifunctional hydroxy-containing compounds and the multifunctional cross-linked compound good compatible with macromolecular compound, thereby the viscosity of resin combination reduces mobile the raising.Thus, in the manufacturing process of flexible printed circuit board, improve to the through hole of the insulated substrate that is arranged at wiring board and the imbedibility of Wiring pattern, therefore can suit as layer flexible wiring board interlayer dielectric, distribution protective membrane.
Herein, with reference to Fig. 1 the summary of the manufacturing process of wiring board of the present invention is described.Shown in Figure 1A, use two sides flexible base, board 10 in the manufacturing of layer flexible wiring board, described two sides flexible base, board 10 possesses insulated substrate 11 and is arranged at Copper Foil 12a on two major surfacess of this dielectric substrate layer 11,12b.At first, at Copper Foil 12a, behind the last lamination dry film of 12b, by exposure and development and the Copper Foil 12a of dry film, Copper Foil 12a is removed in the etching of 12b, and the part of 12b forms through hole 13 at insulated substrate 11 then.Then, form copper coating 14 on the surface of through hole 13, with two sides Copper Foil 12a, 12b is electrically connected (with reference to Figure 1B).
Then, shown in Fig. 1 C, remove the Copper Foil 12b in the zone that becomes flexible part 16 by etching.Then, resin combination of the present invention is filled into carries out insulation processing in the through hole 13.Herein, as mentioned above, in resin combination of the present invention, using polyfunctional isocyanate's compound as multifunctional cross-linked compound, use as macromolecular compound under the situation of the compound with hydroxyl and/or carboxyl, resin combination shows flowability and the viscosity of appropriateness.Thus, even under the situation that small through hole 13 is set, also can be filled in the through hole 13.
Then, shown in Fig. 1 D, at Copper Foil 12a, the last lamination laminate 15 respectively of 12b, the protective layer 15b that described laminate 15 possesses Copper Foil 15a and obtains at this Copper Foil 15a coating resin combination of the present invention.In the resin combination of the present invention, using under the situation of polyimide as macromolecular compound the imidization after not needing to be coated with herein.Thus, do not need the post curing treatment after the lamination, can utilize quick compacting to carry out lamination.
Then, shown in Fig. 1 E, after removing Copper Foil 15a and protective layer 15b by etching etc., apply copper coating 14 and will be as the Copper Foil 15a of outer conductive layers and Copper Foil 12a as internal electrically conductive layer, 12b is electrically connected.Then, utilize subtractive process etc. that Copper Foil 15a patterning is formed Wiring pattern.At last, shown in Fig. 1 F, through the Copper Foil 15a of Wiring pattern processing coating resin combination of the present invention, form protective membrane 17.Herein, as mentioned above, in resin combination of the present invention, using polyfunctional isocyanate's compound as multifunctional cross-linked compound, use as macromolecular compound under the situation of the compound with hydroxyl and/or carboxyl, resin combination shows flowability and the viscosity of appropriateness.Thus, even under the situation that has formed fine Wiring pattern, also can be between Wiring pattern the potting resin composition, can carry out insulation protection.
In addition, resin molding of the present invention wishes that the layer insulation resistance in 85 ℃ of temperature, humidity 85%, 1000 hours insulating reliability test is 10 9More than the Ω, 120 ℃～220 ℃ viscosity is 5000PaS～100000PaS, and having elongation is plasticity part more than 50% less than 20% elastic part and elongation, and the thickness of interlayer insulating film is below the 40 μ m.Thus, resin molding and the resin molding lamination that is formed at Copper Foil during in wiring board, can embedded through-hole section well, the wiring board end does not have resin flows, can suit to use.As under the situation of interlayer dielectric, require resin to flow into wiring part and the through-hole section of wiring board on the one hand, require resin combination not flow out from the end of wiring board on the other hand and to keep to a certain degree.This be because, if attempt fully to flow into to through hole in the suppression process under the high pressure, resin combination can flow out from the end of wiring board usually, the thickness attenuation of the insulation layer of the end of wiring board, insulativity might reduce.Under the situation of said structure, by controlling resin molding in 120 ℃～220 ℃ viscosity and the elastic part of resin molding and plasticity part, can take into account to the inflow of through hole and prevent resin combination flow out from the end of wiring board this 2 point (these 2 be in the prior art be difficult to realize and be opposite), can realize very good imbedibility.
Namely, about the viscosity of resin molding at 120 ℃～220 ℃, between when lamination, use 120 ℃～220 ℃, if viscosity is more than the 5000PaS, then can prevent resin combination from the end outflow of wiring board and obtain good imbedibility, if viscosity is below the 100000PaS, then can be in general lamination device such as for example vacuum pressing machine lamination well.In addition, can prevent that less than 20% elastic part resin combination from flowing out from the end of wiring board at the elongation of resin molding, be that plasticity 50% or more partly can realize better imbedibility at the elongation of resin molding.In addition, the thickness of interlayer insulating film is below the 40 μ m, show extremely good low bounce, the insertion in small portable electronic devices becomes well thus, is 10 by the layer insulation resistance in 85 ℃ of temperature, humidity 85%, 1000 hours insulating reliability test 9More than the Ω, even the thickness of interlayer insulating film is below the 40 μ m, also can obtain the good insulation performance reliability.
Below, the embodiment of the invention described above is elaborated.Need to prove, in the 1st following embodiment～the 4th embodiment, mainly the resin combination to above-mentioned the 2nd mode describes, in the 1st following embodiment～the 4th embodiment, by the employed macromolecular compound of suitable selection, can also be as the resin combination of the 1st mode.
(the 1st embodiment)
As the material that in the manufacturing of flexible printed board, uses, proposed to comprise the resin combination with the polyimide precursor of a part of imidization of polyamic acid.In this resin combination, by using the polyimide precursor with a part of imidization of polyamic acid, can reduce the warpage that accompanies with the contraction of polyimide, can carry out imidization at low temperatures, the polyimide precursor that inhibition and imidization accompany and the reaction of wiring material utilize alkaline aqueous solution to carry out development treatment simultaneously easily.But multifunction and the lightweight of the flexible printed board by in recent years even comprise in use under the situation of resin of existing polyimide precursor, also may not reduce warpage fully, and expectation improve thermotolerance.
As (A) macromolecular compound, the inventor is conceived to use contains polyamic acid structure and polyimide structures as the polyimide this point of structural unit.And; the inventor finds; by containing the polyimide as (A) macromolecular compound; (B) isocyanate compound (blocked isocyanate compounds) of multifunctional hydroxy-containing compounds and conduct (C) multifunctional cross-linked compound; and the mol ratio that makes the isocyanate group that hydroxyl that multifunctional hydroxy-containing compounds contains and blocked isocyanate compounds contain is in pre-determined range; the reduction of the warpage in the time of can realizing solidifying and excellent thermotolerance can access the surface protection film that can suit as semiconductor element; interlayer dielectric; use in printed circuit board protection insulating film; the resin combination of the material of interlayer dielectric etc.
In this resin combination, multifunctional hydroxy-containing compounds does not enter in the skeleton of polyimide and exists as second composition, between multifunctional hydroxy-containing compounds and blocked isocyanate compounds, form three-dimensional cross-linked, the contraction of the molecular chain of the polyimide in the time of therefore can suppressing to solidify, can suppress warpage, the melt viscosity of the resin combination before solidifying is reduced, and the through hole imbedibility improves.In addition, polyimide has polyamic acid structure (this polyamic acid has heat cross-linking functional group) as structural unit, and therefore being situated between between multifunctional hydroxy-containing compounds and blocked isocyanate compounds has formed three-dimensional network by polyimide.Thus, the warpage in the time of can reducing curing.In addition, the consistency of polyimide and other compositions is good, have the polyimide structures of formation three-dimensional structure or inierpeneirating network structure [InterPenetration Network (IPN)] as structural unit, thereby show high heat resistance (for example, high solder heat resistance).In addition, by comprising blocked isocyanate compounds, can make the carboxyl inerting at low temperatures, can carry out low-temperature curing, the contraction of the polyimide skeleton in the time of therefore can preventing from solidifying can suppress warpage.Below, the 1st embodiment of the present invention is specifically described.
The resin combination of the 1st embodiment of the present invention contains (a) polyimide, (B) multifunctional hydroxy-containing compounds and (c-1) isocyanate compound (blocked isocyanate compounds), polyimide has polyimide structures and polyamic acid structure as structural unit, and the mol ratio of the isocyanate group that the hydroxyl that multifunctional hydroxy-containing compounds contains and blocked isocyanate compounds contain is hydroxyl/isocyanate base=0.5～1.
In this resin combination, the mol ratio of the isocyanate group that the hydroxyl that multifunctional hydroxy-containing compounds contains and blocked isocyanate contain is hydroxyl/isocyanate base=0.5～1, and the amount of isocyanate group is excessive with respect to hydroxyl.Constitute by this, infer to show thermotolerance by following mechanism.Isocyanate group and hydroxyl reaction and form the carboxylamine ester structure, but the amount of isocyanate group is excessive with respect to hydroxyl, thereby the isocyanate group residue.The carboxyl reaction of the polyamic acid structure that contains in the remaining polyimide after remaining isocyanate group and the imidization reaction forms amide structure and urea structure etc.That is, think between polyimide and blocked isocyanate compounds, to form chemically crosslinked by thermofixation, and between multifunctional hydroxy-containing compounds and blocked isocyanate compounds, form chemically crosslinked.Like this, utilize two or more crosslinked such as isocyanic ester reaction each other and form three-dimensional network, thereby further show thermotolerance.
Then, each constitutive requirements that constitutes resin combination are elaborated.
(a) polyimide
The polyimide that is used for the resin combination of present embodiment for example can obtain by making tetracarboxylic dianhydride and diamine reactant.To employed tetracarboxylic dianhydride without limits, can use existing known tetracarboxylic dianhydride.As the tetracarboxylic dianhydride, can be suitable for aromatic tetracarboxylic acid and aliphatics tetracarboxylic dianhydride etc.In addition, to employed diamines without limits, can use existing known diamines.
Concrete example as the aromatic tetracarboxylic acid; 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; 3,3 '; 4; 4 '-benzophenone tetracarboxylic dianhydride; 2,2 ', 3; 3 '-benzophenone tetracarboxylic dianhydride; 2; two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2-; 2,2-two (2; 3-dicarboxyl phenyl) propane dianhydride; 1; two (3,4-dicarboxyl phenyl) the ethane dianhydrides of 1-; 1,1-two (2; 3-dicarboxyl phenyl) ethane dianhydride; two (3; 4-dicarboxyl phenyl) methane dianhydride; two (2,3-dicarboxyl phenyl) methane dianhydride; two (3,4-dicarboxyl phenyl) sulfone dianhydride; 3; the two O-phthalic acid dianhydrides of 3 '-oxygen; 4; the two O-phthalic acid dianhydrides of 4 '-oxygen; two (4-(4-amino-benzene oxygen) phenyl) propane of 2,2-; 1,3-dihydro-1; 3-dioxo-5-isobenzofuran carboxylic acid-1; 4-phenylene ester; 4-(2,5-dioxo tetrahydrofuran (THF)-3-yl)-1,2; 3; 4-naphthane-1, the 2-dicarboxylic 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; 2,2-two (3; 4-dicarboxyl phenyl) hexafluoropropane dianhydride; 2; two (4-(3, the 4-di carboxyl phenyloxy) phenyl) hexafluoropropane dianhydrides of 2-; 2,2-is two, and (4-(3; 4-dicarboxyl benzoyl oxygen base) hexafluoropropane dianhydride phenyl); 2; 2 '-two (trifluoromethyl)-4,4 '-two (3,4-di carboxyl phenyloxy) biphenyl acid acid anhydride etc.
As aliphatics tetracarboxylic dianhydride's concrete example, can enumerate tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,5,6-hexanaphthene tetracarboxylic dianhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic acid dianhydride, dicyclo [2,2,2] suffering-7-alkene-2,3,5,6 tetracarboxylic dianhydrides, 1,2,3,4-butane tetracarboxylic acid dianhydride etc.
Above-mentioned tetracarboxylic dianhydride may be used alone, can also be 2 or more kinds in combination.Need to prove, from the thermotolerance of polyimide and the aspect of polymerization velocity, in above-mentioned tetracarboxylic dianhydride, as particularly preferred material, can enumerate 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 4, the two O-phthalic acid dianhydrides, 3 of 4 '-oxygen, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride.
Concrete example as diamines, for example can enumerate 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 3,3 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, two (3-(3-amino-benzene oxygen) phenyl) ether, two (4-(4-amino-benzene oxygen) phenyl) ether, 1, two (3-(3-amino-benzene oxygen) phenoxy group) benzene of 3-, 1, two (4-(4-amino-benzene oxygen) phenoxy group) benzene of 4-, two (3-(3-(3-amino-benzene oxygen) phenoxy group) phenyl) ether, two (4-(4-(4-amino-benzene oxygen) phenoxy group) phenyl) ether, 1, two (3-(3-(3-amino-benzene oxygen) phenoxy group) phenoxy group) benzene of 3-, 1, two (4-(4-(4-amino-benzene oxygen) phenoxy group) phenoxy group) benzene of 4-, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, 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 of 2-, 1,1,3,3, the 3-HFC-236fa, 2, two [4-(4-amino-benzene oxygen) phenyl]-1 of 2-, 1,1,3,3, the 3-HFC-236fa, mphenylenediamine, O-Phenylene Diamine, 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, 2, two [4-(3-amino-benzene oxygen) phenyl] butane of 2-, α, ω-two (2-amino-ethyl) polydimethylsiloxane, α, ω-two (3-aminopropyl) polydimethylsiloxane, α, ω-two (the amino butyl of 4-) polydimethylsiloxane, α, ω-two (4-aminophenyl) polydimethylsiloxane, α, the poly-diphenyl siloxane of ω-two (3-aminopropyl) etc., but be not limited to these.Be preferably 4,4 '-two (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-, polyoxyalkylene diamines.
In addition, as diamines, preferred α also, ω-two (2-amino-ethyl) polydimethylsiloxane, α, ω-two (3-aminopropyl) polydimethylsiloxane, α, ω-two (the amino butyl of 4-) polydimethylsiloxane, α, ω-two (4-aminophenyl) polydimethylsiloxane, α, the poly-diphenyl siloxane of ω-two (3-aminopropyl) etc.
In above-mentioned diamines, consider from the aspect of the warpage of the cured article that reduces resin combination, preferably use polyethyleneoxide diamine, polypropyleneoxide diamine, other comprise the polyoxyalkylene diamines etc. of the different oxyalkylene alkyl of carbochain number.As the polyoxyalkylene diamines class, can enumerate the material etc. that polypropyleneoxide diamine, JEFFAMINE XTJ-542, XTJ533, XTJ536 etc. such as polyetheramine D-230, D-400 that polyethyleneoxide diamine such as JEFFAMINE ED-600, ED-900 that U.S. Huntsman society makes, ED-2003, EDR-148, HK-511, JEFFAMINE D-230, D-400, D-2000, D-4000, German BASF society make, D-2000 have the polytetramethylene vinyl.
Wherein, the EDR-148 that molecular weight ratio is lower, D-230, D-400, HK-511 etc. can form the polymkeric substance that has than high glass transition, therefore preferably use in the purposes that needs thermotolerance, chemical proofing.On the other hand, the higher excellences such as flexibility such as D-2000 of molecular weight ratio.In addition, consider that from the aspect of the balance of thermotolerance, chemical proofing and flexibility, solvent soluble the weight-average molecular weight as polyoxyalkylene diamines is preferably 400～3000, be preferably 400～2000 especially, preferably use D-400, D-2000, ED-600, ED-900, XTJ-542.
The polyimide that is used for the resin combination of present embodiment has polyimide structures and polyamic acid structure as structural unit.By having the polyimide structures part and polyamic acid structure division with heat cross-linking functional group good with other composition consistencies so simultaneously, remaining carboxyl inerting in the time of can utilizing reaction with blocked isocyanate to make low-temperature curing suppresses warpage by blocked isocyanate and multifunctional hydroxy-containing compounds.
In addition, the polyimide as the resin combination that is used for present embodiment preferably comprises the polyimide with polyether structure.This be because, by in skeleton, having polyether structure, can control second-order transition temperature and the Young's modulus of the cured article after the thermofixation, can further reduce warpage.In addition because, after thermofixation, at the polyimide with polyether structure and have between the compound of heat cross-linking functional group and form chemically crosslinked, the polyimide that has polyether structure simultaneously has polyoxyalkylene chain, thereby utilize the interaction of the part between macromolecular chain to form three-dimensional network, can show thermotolerance.
In addition, as polyimide, the preferred polyimide that uses the polyimide part that comprises the structure with following general formula (2).This is in order to improve the solvent soluble of polyimide.
General formula (2)
Figure BDA00003375991600241
(in the formula (2), Z 1And Z 2The organic group of representing 4 valencys.Y 1, Y 2, Y 3, Y 4And Y 5The expression carbonatoms is that 1～carbonatoms is 5 alkylidene group, can have side chain.B, c and d represent 1～50 integer.)
In addition, as polyimide, also preferred use comprises the polyimide of the polyimide part of the structure with following general formula (11).By comprising the polyimide part of the structure with following general formula (11), the solvent soluble of polyimide also improves.As polyimide, the preferred polyimide that uses the polyimide part that comprises the structure with above-mentioned general formula (2) or following general formula (11).
General formula (11)
Figure BDA00003375991600242
(in the formula (11), Z 5And Z 6The organic group of representing 4 valencys.Y 6, Y 7, Y 8, Y 9, Y 10, Y 11, Y 12And Y 13The expression alkyl.G represents 3～100 integer.)
In the above-mentioned general formula (2), Y 1, Y 2, Y 3, Y 4, Y 5Be that carbonatoms is that 1～carbonatoms is 5 alkylidene group, for example, can enumerate methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylene.B, c and d represent 1～50 integer, are preferably 3～40, more preferably 5～30.
In the above-mentioned general formula (11), Z 5And Z 6The organic group of representing 4 valencys for example, can be enumerated phenyl, xenyl, phenylbenzene ether, benzophenone base, diphenyl sulfone, naphthyl.Wherein, be preferably xenyl, phenylbenzene ether, benzophenone base, diphenyl sulfone, more preferably the phenylbenzene ether.
In addition, in the above-mentioned general formula (11), Y 6, Y 7, Y 8, Y 9, Y 10, Y 11, Y 12And Y 13The expression alkyl.As Y 6, Y 7, for example, can enumerate carbonatomss such as methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylene is that 1～carbonatoms is 5 alkylidene group.In addition, as Y 8, Y 9, Y 10, Y 11, Y 12And Y 13, for example, can enumerate methyl, ethyl, propyl group, butyl, phenyl.Wherein, be preferably methyl, ethyl, propyl group, butyl, more preferably methyl, ethyl, propyl group.G represents 3～100 integer, is preferably 5～70, more preferably 10～50.
In addition, in the whole diamines in polyimide, the content of diamines with structure of following general formula (12) is preferably above 85 moles below the % of 15 moles of %.This is in order to improve solvent soluble and the low elastic modulusization of polyimide.
General formula (12)
Figure BDA00003375991600251
(in the formula (12), Y 1, Y 2, Y 3, Y 4And Y 5The expression carbonatoms is that 1～carbonatoms is 5 alkylidene group, can have side chain.B, c and d represent 1～50 integer.)
Need to prove, in the above-mentioned general formula (12), from the aspect of the adaptation of substrate, Y 2, Y 3, Y 4And Y 5Preferably has two or more alkylidene groups.
In addition, in the whole diamines in polyimide, the content of diamines that preferably has the structure of following general formula (13) is above 95 moles below the % of 15 moles of %.This is in order to improve solvent soluble and the low elastic modulusization of polyimide.
General formula (13)
Figure BDA00003375991600252
(in the formula (13), Y 6, Y 7, Y 8, Y 9, Y 10, Y 11, Y 12And Y 13The expression alkyl.G represents 3～100 integer.)
In addition, imidization rate as above-mentioned polyimide, consider with the crosslinked aspect as the isocyanate compound of the multifunctional cross-linked compound with bridging property functional group from forming polyimide, be preferably more than 25% less than 100%, more preferably more than 25% below 98%.If the imidization rate of polyimide is below 98%, then with the polyimide precursor of the compound crosslink with heat cross-linking functional group in carboxyl fully residual, therefore after curing, can bring into play chemical proofing, thermotolerance.In addition, if the imidization rate of polyimide is more than 25%, the carboxyl residue that dissolves in alkaline solution after then solidifying tails off, and can bring into play chemical proofing, thermotolerance.
Need to prove, in the above-described embodiment, resin combination to above-mentioned the 2nd mode of having used the polyimide that contains polyimide structures and polyamic acid structure is illustrated, but also can be by in reaching the scope of effect of the present invention, using the polyimide that does not comprise the polyamic acid structure in fact, the resin combination that is used as above-mentioned the 1st mode uses.Under this situation, the imidization rate of polyimide is 100%, does not therefore need imidization reaction just can suppress the deterioration of wiring layer, brings into play good insulation performance reliability, thermotolerance.
Then, the manufacture method to polyimide describes.The manufacture method of the polyimide of present embodiment can be suitable for all method that can make polyimide that comprises known method.Wherein, the preferred method of in organic solvent, reacting of using.As solvent used in such reaction, for example, can enumerate N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, 1,2-glycol dimethyl ether, tetrahydrofuran (THF), 1,3-dioxane, 1,4-dioxane, dimethyl sulfoxide (DMSO), benzene,toluene,xylene, trimethylbenzene, phenol, cresols, ethyl benzoate, butyl benzoate etc.These are used alone or two or more kinds mixed.Need to prove that the concentration of the reaction raw materials in this reaction is generally 2 quality %～80 quality %, be preferably 30 quality %～70 quality %.
The tetracarboxylic dianhydride who reacts and the mol ratio of diamines are in 0.8～1.2 scope.Under the situation in this scope, 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 is preferably more than 5000 below 100000.Herein, weight-average molecular weight refers to, the polystyrene of known number average molecular weight is utilized the weight-average molecular weight of gel permeation chromatography as standard.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, then use the warpage of the protective membrane that resin combination obtains to improve low bounce and excellent heat resistance.Can there be printing during this external coating and printing with desired thickness with oozing out, and the mechanical properties excellences such as elongation of resulting protective membrane.
Polyimide utilizes following method to obtain.At first reaction raw materials is at room temperature carried out polycondensation, make the polyimide that is constituted by the polyamic acid structure thus.Then, this polyimide preferably is heated to 100 ℃～400 ℃ carries out imidization, perhaps use imidization agent such as diacetyl oxide to carry out chemical imidization, obtain comprising the polyimide of the polyimide structures with repeat unit structure corresponding with polyamic acid thus.Carry out in heating under the situation of imidization, in order to remove the water that by-product is given birth to, also preferred coexistence entrainer (being preferably toluene and dimethylbenzene) uses Dean Stark type dewatering unit, dewaters under refluxing.
In addition, also preferably react at 80 ℃～220 ℃, comprise generation and the hot imide reaction of the polyimide of polyamic acid structure thus simultaneously, obtain comprising the polyimide of polyimide structures and polyamic acid structure.That is, also preferably two amine components and dicarboxylic anhydride composition are suspended or be dissolved in the organic solvent, under 80 ℃～220 ℃ heating, make its reaction, carry out generation and the dehydration imidization of polyimide simultaneously, obtain polyimide thus.
In addition, the end of the main polymer chain of polyimide can also carry out end-blocking with the end-capping reagent that is made of monoamine derivative or carboxylic acid derivative.Seal by the end to the main polymer chain of polyimide, become excellent from the storage stability of functional end-group.
As the end-capping reagent that is constituted by the monoamine derivative, for example, can enumerate aniline, Ortho Toluidine, meta-aminotoluene, para-totuidine, 2, the 3-xylidine, 2, the 6-xylidine, 3, the 4-xylidine, 3,5-xylidine, Ortho-Chloro aniline, m-chloro aniline, p-Chlorobenzoic acid amide, o-bromoaniline, m-bromoaniline, para-bromoaniline, o-Nitraniline, p-Nitroaniline, m-nitraniline, Ortho-Aminophenol, p-aminophenol, Metha Amino Phenon, o-anisidine, m-anisidine, P-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o-Aminobenzaldehyde, p-Aminobenzaldehyde, NSC 36957, adjacent aminobenzonitrile, the p-aminophenyl nitrile, the m-aminophenyl nitrile, the 2-phenylaniline, the 3-phenylaniline, the 4-phenylaniline, 2-aminophenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, the 2-aminobenzophenone, the 3-aminobenzophenone, the 4-aminobenzophenone, 2-aminophenyl phenyl thioether, 3-aminophenyl phenyl thioether, 4-aminophenyl phenyl thioether, 2-aminophenyl phenylsulfone, 3-aminophenyl phenylsulfone, 4-aminophenyl phenylsulfone, 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, the 1-amino anthracene, the 2-amino anthracene, aromatic series monoamines such as 9-amino anthracene.Wherein, preferably use the derivative of aniline.These may be used alone, can also be 2 or more kinds in combination.
As the end-capping reagent that is constituted by carboxylic acid derivative, mainly can enumerate the carboxylic acid anhydride derivative.As the carboxylic acid anhydride derivative, for example, can enumerate Tetra hydro Phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyl phenyl ether acid anhydride, 3,4-dicarboxyl phenyl ether acid anhydride, 2,3-diphenyl dicarboxylic acid acid anhydride, 3,4-diphenyl dicarboxylic acid acid anhydride, 2,3-dicarboxyl phenyl sulfone acid anhydride, 3,4-dicarboxyl phenyl sulfone acid anhydride, 2,3-dicarboxyl phenyl thioether acid anhydride, 3,4-dicarboxyl phenyl thioether acid anhydride, 1,2-naphthalene dicarboxylic acids acid anhydride, 2,3-naphthalene dicarboxylic acids acid anhydride, 1,8-naphthalene dicarboxylic acids acid anhydride, 1,2-anthracene dicarboxylic anhydride, 2,3-anthracene dicarboxylic anhydride, aromatic dicarboxylic acid acid anhydrides such as 1,9-anthracene dicarboxylic anhydride.In these aromatic dicarboxylic acid acid anhydrides, preferably use Tetra hydro Phthalic anhydride.These may be used alone, can also be 2 or more kinds in combination.
The polyimide that utilizes aforesaid method to obtain can not carry out desolventizing and directly (perhaps further be mixed necessary solvent, additive etc. are back) be used for the resin combination of present embodiment.
Need to prove, in the above-described embodiment, to having used polyimide to be illustrated (described polyimide has the polyimide structures that comprises the aliphatie diamine composition and polyamic acid structure as structural unit) as the resin combination of the 2nd mode of (A) macromolecular compound, but also can be by in reaching the scope of effect of the present invention, using the polyimide that does not comprise the polyamic acid structure in fact, the resin combination that is used as above-mentioned the 1st mode uses.
(B) multifunctional hydroxy-containing compounds
The multifunctional hydroxy-containing compounds that is used for the resin combination of present embodiment refers to comprise with respect to a molecular chain material of 2 above hydroxyls.Can enumerate the material of alkyl such as comprising aliphatics, aromatic series, alicyclic radical in the skeleton, consider from the aspect that improves insulativity, the material that preferably has the structure of following formula (14) expression in skeleton is considered from the aspect that suppresses warpage, is preferably to comprise aliphatic compound.This is because by having aliphatic skeleton, can suppress water absorbability and do not damage the effect that suppresses warpage, even also can show high-insulativity when moisture absorption.Need to prove that the effect that suppresses warpage under the situation of the aliphatic group that comprises long-chain improves, thereby preferred.
General formula (14)
(in the formula (14), X represents aromatic series, Y represent carbonatoms be 1 to carbonatoms be 10 aliphatics, Z represents to be selected from the functional group in ether, ester group, carbonate group, carbamate groups, the urea groups, the integer of h=0～2, the integer of i=0～1, the integer of j=1～1000.)
In addition, the material that particularly in the electronic material purposes, does not preferably comprise halogens such as fluorine, chlorine.
As the concrete example of multifunctional hydroxy-containing compounds, can enumerate polybutadiene diol such as PTMG1000 polytetramethylene glycol such as (manufacturings of Mitsubishi Chemical society), G-1000 (Japanese Cao Da society make); Hydrogenated butadiene polymer glycol such as GI-1000 (Japanese Cao Da society make); DURANOL T5651, DURANOL T5652, DURANOL T4671 (chemistry society of Asahi Chemical Industry makes) and PRAXCELL CD polycarbonate diols such as (manufacturings of Daicel Chemical society); PRAXCELL200 polycaprolactone glycols such as (manufacturings of Daicel Chemical society); Dihydroxyphenyl propane bisphenols such as (manufacturings of Daicel Chemical society); A Hydrogenated Bisphenol A classes such as Rikabinol HB (new Japanese physics and chemistry society make) etc.
Wherein, consider from the aspect that improves insulativity, be preferably polybutadiene diol, hydrogenated butadiene polymer glycol, polycarbonate diol, consider from the aspect that reduces warpage, be preferably polycarbonate diol.
In addition, aspect reducing warpage and deliquescent organic solvent, consider that multifunctional hydroxy-containing compounds preferably at room temperature be liquid state.As molecular weight, be preferably 500～3000, special preferred molecular weight is 500～2000.
Consider that from taking into account the aspect that reduces warpage, solder heat resistance and chemical proofing multifunctional hydroxy-containing compounds preferably contains 3 mass parts～70 mass parts with respect to resin combination 100 mass parts, more preferably contains 5 mass parts～60 mass parts.
Need to prove, in the present embodiment, as (B) multifunctional hydroxy-containing compounds, the multifunctional hydroxy-containing compounds that contains 2 hydroxyls is illustrated, can also in reaching the scope of effect of the present invention, use polyvalent alcohol that contains 2 above hydroxyls etc.
(c-1) blocked isocyanate compounds
The blocked isocyanate compounds that is used for the resin combination of present embodiment refers to the compound that obtains by the isocyanate reaction that makes end-capping reagent and intramolecularly have 2 above isocyanate group.The isocyanate compound that has 2 above isocyanate group as intramolecularly, can enumerate 1, the 6-hexane diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2, the 4-toluenediisocyanate, 2, the 6-toluenediisocyanate, eylylene diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, 4,4 '-hydroxide vulcabond, isophorone diisocyanate, 1, the 5-naphthalene diisocyanate, 4, the 4-diphenyl diisocyanate, 1, two (isocyanato-methyl) hexanaphthenes of 3-, phenylene 1, the 4-vulcabond, phenylene 2, the 6-vulcabond, 1,3,6-hexa-methylene triisocyanate, perhaps hexamethylene diisocyanate etc.As end-capping reagent, can enumerate alcohols, phenol, ε-Ji Neixianan, oximes, active methylene group class, thio-alcohol, amine, acid imide, amides, imidazoles, ureas, Carbamates, imines class or sulfites, etc.
Concrete example as blocked isocyanate compounds, can enumerate hexamethylene diisocyanates such as trade(brand)name DURANATE SBN-70D, TPA-B80E that Asahi Chemical Industry chemistry society makes, TPA-B80X, 17B-60PX, MF-B60X, E402-B80T, ME20-B80S, MF-K60X, K6000 (below, be also referred to as " HDI ") is blocked isocyanate.In addition, as Mitsui Chemicals urethane society goods, can enumerate trade(brand)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 CORONET AP-M2503,2515,2507 that Japanese polyurethane industry society makes, 2513 or Millionate MS-50 etc., be the model 7950,7951 made of the Baxenden society of blocked isocyanate, 7990 etc. as isophorone diisocyanate.These blocked isocyanate compounds can be used separately, also can be used in combination of two or more.
Need to prove, in the present embodiment, as (C) multifunctional cross-linked compound, the example that has used blocked isocyanate compounds is illustrated, can also use above-mentioned polyfunctional isocyanate's compound with 2 above isocyanate group to replace blocked isocyanate compounds.In addition, can also in reaching the scope of effect of the present invention, use Duo Guan Neng oxazoline compound to replace polyfunctional isocyanate's compound.
Need to prove that except polyimide, multifunctional hydroxy-containing compounds, blocked isocyanate compounds, resin combination can also contain organic solvent.This be because, be dissolved in the state of organic solvent by formation, can use preferably as varnish.
As such organic solvent, can enumerate N, the N-N,N-DIMETHYLACETAMIDE, N, the N-diethyl acetamide, N, dinethylformamide, N, the N-diethylformamide, amide solvents such as N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, ester solvent in the γ-Wu Neizhi etc., dimethyl sulfoxide (DMSO), diethyl sulfoxide, sulfur-bearing series solvents such as hexamethyl sulfoxide, cresols, phenol series solvents such as phenol, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethyleneglycol dimethyl ether, dioxane, tetrahydrofuran (THF), butyl benzoate, ethyl benzoate, ether solvents such as methyl benzoate.In addition, these organic solvents can use separately, also can share two or more.Particularly, consider from the aspect of high boiling point and low water absorbable, preferably use gamma-butyrolactone, triglyme, butyl benzoate, ethyl benzoate.
(F) fire retardant
Resin combination can also contain fire retardant.Kind to fire retardant is not particularly limited, and can enumerate halide, P contained compound and inorganic combustion inhibitor etc.These fire retardants can use a kind of, also can be use mixing two or more.Addition to fire retardant is not particularly limited, can the suitable change according to the kind of employed fire retardant.For example, can use in the scope of 5 quality % to 50% with the content of polyimide as benchmark.
As halide, can enumerate the organic compound that comprises chlorine and the compound that comprises bromine etc.Specifically, can enumerate pentabromo-diphenyl ether, octa-BDE, decabromodiphynly oxide, tetrabromo-bisphenol, hexabromocyclododecane tetrabromo-bisphenol etc.
As P contained compound, can enumerate phosphorus compounds such as phosphine nitrile, phosphine, phosphine oxide, phosphoric acid ester and phosphorous acid ester.Particularly from the aspect of the consistency of polyimide compositions, preferably use phosphine nitrile, phosphine oxide or phosphoric acid ester.
As the concrete example of P contained compound, can enumerate volt and see the phosphine carbonitrile derivatives FP100 of society of pharmacy institute manufacturing, FP110, FP300, FP400 etc.
As inorganic combustion inhibitor, 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.Need to prove that by share antimony compounds and above-mentioned halide, weisspiessglanz is extracted halogen atom out and generated antimony halides from fire retardant in the heat decomposition temperature zone of plastics, therefore can improve flame retardant resistance synergistically.
Inorganic combustion inhibitor is not dissolved in organic solvent, so the particle diameter of its powder is preferably below the 100 μ m.This be because, if particle diameter is below the 100 μ m, sneak into easily in the polyimide compositions, can not damage the transparency of the resin after the curing.In order to improve flame retardant resistance fully, the particle diameter of powder is preferably below the 50 μ m, is preferably especially below the 10 μ m.
In addition, as fire retardant, can use nitrogenous compound.Nitrogenous compound can be with a kind of as fire retardant, also can mix two or more with nitrogenous compound above-mentioned halide, P contained compound and inorganic combustion inhibitor and is used as fire retardant.Addition as nitrogenous compound is not particularly limited, and can change according to the kind of employed fire retardant.As the addition of nitrogenous compound, for example, with above-mentioned fire retardant similarly, can in the scope of 5 quality % to 50 quality %, use with the content of polyimide as benchmark.As nitrogenous compound, for example, can enumerate the melamine cyanurate of the manufacturing of the chemical society of daily output, the manufacturing of Sakai chemical industry society etc.
When forming coated film, carry out viscosity and thixotropic adjustment according to its coating method.As required, use after can also adding filler and thixotropy imparting agent.In addition, can also add additives such as known defoamer, flow agent and pigment.
In addition, when forming coated film, can add the urethane catalyzer and use.As the urethane catalyzer, can enumerate U-CAT SA (registered trademark) 102,603,506, U-CAT (registered trademark) 1102 that San-Apro society makes, organic zirconate, nanmu that Matsumoto Fine Chemicals society makes and originally change into zirconium K-KAT that society makes etc.
Resin combination can also contain the compound with heat cross-linking functional group.As the compound with heat cross-linking functional group, can enumerate triazine based compound, benzoxazine compound and epoxy compounds etc.
As the triazine based compound, be preferably melamine class and melamine cyanurate class.As melamine class, can enumerate melamine derivative, have the compound of similar structure and the condenses of trimeric cyanamide etc. with trimeric cyanamide.As the concrete example of melamine class, for example, can enumerate methylolation trimeric cyanamide, melon, cyanurodiamide, formoguanamine, amidino groups trimeric cyanamide, cyano group trimeric cyanamide, aryl guanamines, melam, melem, trimerization dicyan acetonitrile etc.As the melamine cyanurate class, can enumerate the reaction with same mole thing of cyanuric acid and melamine class.In addition, several amino in the melamine cyanurate class or hydroxyl can be replaced by other substituting groups.Benzoxazine compound can only be made of monomer, also can the several molecule polymerization form the oligopolymer state.In addition, can also use the benzoxazine compound with different structure simultaneously.Wherein, preferably use the bis-phenol benzoxazine.
Need to prove that resin combination can be used as negative light-sensitive resin combination by further adding Acrylic Acid Monomer and optical free radical initiator and use.In addition, can be used as the positive type photosensitive organic compound use by adding light acid producing agent.
By heating above-mentioned resin combination, can access cured article.Mode to heating is not particularly limited, and preferably the temperature province in 2 stages heated respectively 5 minutes～60 minutes, more preferably, heats 15 minutes～60 minutes at 160 ℃～200 ℃ after 5 minutes～60 minutes 100 ℃～130 ℃ heating.By two kinds of temperature provinces it being solidified like this, can control the reaction between the compound that contains in the resin combination, form three-dimensional network.And, can improve thermotolerance and the chemical proofing of cured article thus.More particularly, as described below.At first, mainly be that multifunctional hydroxy-containing compounds and blocked isocyanate compounds are reacted and generation carboxylamine ester structure at low-temperature region (for example 100 ℃～130 ℃).Chemically crosslinked I between multifunctional hydroxy-containing compounds and the blocked isocyanate compounds forms (hereinafter as " operation (I) ") thus.At high-temperature area (for example 160 ℃～200 ℃) mainly be imidization reaction that polyimide take place thereafter.And imidization and carboxylic acid and the isocyanate group of polyamic acid in the remaining polyimide react does not form amide structure, urea structure etc.Thus, the chemically crosslinked II between polyamic acid and the isocyanic ester forms (hereinafter as " operation (II) ").Utilize the three-dimensional network that forms by this crosslinked I and crosslinked II, can access the cured article of excellent heat resistance.Need to prove, form crosslinked II after remaining isocyanate group react each other in remaining isocyanate group.Spike disappears thus, and the insulativity of cured article improves.
In above-mentioned operation (II), also depend on the thickness of formed resin combination film, utilize baking oven or hot-plate that top temperature is made as 150 ℃～220 ℃ scope, heating is 5 minutes～100 minutes under inert atmospheres such as air or nitrogen, thus desolventizing.Heating temperature can be constant in the time in entire treatment, also can heat up at leisure.The resin combination film can utilize known silk screen printing or precise glue dispensing method in flexible printed circuit substrate and semiconductor wafer surface printing and form.
Resin combination demonstrates excellent thermotolerance by thermofixation; therefore useful as the surface protection film of the surface cure film of semiconductor element, interlayer dielectric, bonding sheet, use in printed circuit board protection insulating film, tellite etc., be applicable to various electronic units.For example, as the tellite of flexibility, use ESPANEX M (chemistry society of Nippon Steel makes) (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 also makes its curing.Can be used as the outside terminal use by implement electronickelling-Jin in uncoated part.The surface protection film of Xing Chenging can be brought into play the good insulation performance characteristic like this.Need to prove that the thermofixation of the resin combination in the present embodiment is carried out under lower temperature condition (for example 160 ℃～200 ℃), therefore the oxidation that does not produce copper.Can carry out such low-temperature curing is because therefore carboxylic acid and blocked isocyanate compounds (speak by the book, end-blocking is through adding the isocyanate compound of heat extraction) reaction does not need imidization completely, does not need 250 ℃ heat.
In addition, the resin combination of present embodiment can be used as resin molding and uses by coating on the base material and drying.
In addition; use the two sides copper foil laminate of ESPANEX M (chemistry society of Nippon Steel makes) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)); make two face component circuit substrate is installed; coating resin composition and curing beyond the parts installation portion of this circuit substrate; when resin combination is used as surface protection film, also can bring into play the good insulation performance characteristic.Herein, the thickness of surface protection film is preferably 1 μ m～50 μ m.This be because, be more than the 1 μ m by making thickness, handle to become easily, by being below the 50 μ m, bending is easily installed and is become easy.
Need to prove that the resin combination of present embodiment can also use as photosensitive polymer combination by containing (D) sensitizer.In addition, by photosensitive polymer combination is coated on the base material, can also obtain photosensitive film.
In addition, the resin combination of present embodiment is by arranging resin combination and dry at Copper Foil, can be aptly as the interlayer dielectric of layer flexible wiring board etc.In addition, the resin combination of present embodiment arranges resin combination by the wiring trace that is formed on the base material with covering, can be used as the protective membrane of the Wiring pattern of wiring board aptly.
(the 2nd embodiment)
In the manufacturing process of flexible printed board, need the tectum of electrical insulation reliability, anti-bending, thermotolerance, excellent in flame retardance.In order to realize such tectum, proposed to comprise and used aliphatie diamine as the resin combination of the polyamic acid of two amine components.In this resin combination, because polyamic acid contains aliphatie diamine, thereby the molecular weight that makes resin combination be dissolved in the varnish in the solvent reduce to become big, because the reduction of the residual film ratio when utilizing lithography to form pattern and the distortion of pattern form etc., development reduces sometimes.
The inventor be conceived to use have the polyimide structures that comprises the aliphatie diamine composition and polyamic acid structure as the polyimide of structural unit as (A) macromolecular compound this point.And, the inventor finds, by contain as (A) macromolecular compound have the polyimide structures that comprises the aliphatie diamine composition and polyamic acid structure as 2 officials of the polyimide of structural unit, the multifunctional hydroxy-containing compounds of conduct (B) can hydroxy-containing compounds, the blocked isocyanate compounds of the multifunctional cross-linked compound of conduct (C) and (D) sensitizer, can realize development property and warpage well, photosensitive composite with insulativity of excellence.
In this photosensitive polymer combination, the hydroxyl that 2 officials can hydroxy-containing compounds and the isocyanic ester radical reaction of blocked isocyanate compounds and form the carboxylamine ester structure, and 2 officials can not enter in the polyimide skeleton by hydroxy-containing compounds, and exist as second composition in photosensitive polymer combination.Thus, the contraction of the polyimide skeleton in the time of can preventing from solidifying can reach the reduction of warpage.In addition, owing to comprise the aliphatie diamine composition in the polyimide structures of polyimide, thereby the molecular weight that can suppress due to the depolymerization of polyamic acid structure reduces.Thus, molecular weight stabilization, thereby the reduction of residual film ratio and the distortion of pattern form can suppress to utilize lithography to form pattern the time can suppress the reduction of development property.Below, the 2nd embodiment of the present invention is specifically described.
The photosensitive polymer combination of the 2nd embodiment of the present invention contains (a) polyimide, (b) 2 officials energy hydroxy-containing compounds, (c-1) isocyanate compound (blocked isocyanate compounds) and sensitizer, and the mol ratio of the isocyanate group that the hydroxyl that 2 officials energy hydroxy-containing compounds contains and blocked isocyanate compounds contain is hydroxyl/isocyanate base=0.5～1.
In this resin combination, the mol ratio of the isocyanate group that the hydroxyl that 2 officials can hydroxy-containing compounds be contained and blocked isocyanate compounds contain is hydroxyl/isocyanate base=0.5～1, thus the carboxylic acid reaction of the polyamic acid structure that contains of excessive isocyanate group and polyimide.Thus, form three-dimensional network, can realize excellent insulating reliability.Below, each constitutive requirements is elaborated.
(a) polyimide
At first, the polyimide in the photosensitive polymer combination of present embodiment is described.In the photosensitive polymer combination of present embodiment, polyimide for example can obtain by making tetracarboxylic dianhydride and diamine reactant.To employed tetracarboxylic dianhydride without limits, can use existing known tetracarboxylic dianhydride.As the tetracarboxylic dianhydride, can be suitable for aromatic tetracarboxylic acid and aliphatics tetracarboxylic dianhydride etc.In addition, to employed diamines without limits, can use existing known diamines.
In the photosensitive polymer combination of present embodiment, as polyimide, from the aspect of development and molecular weight stability, preferably has the polyamic acid structure of the polyimide structures of following general formula (3) expression and following general formula (4) expression respectively as repeated structural unit.
General formula (3)
Figure BDA00003375991600341
General formula (4)
(in formula (3) and the formula (4), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency, can be the same or different.R 3, R 6, R 9, R 12And R 15The expression carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, and m, n, p represent the integer below 100 more than 0 independently of one another.R 16The organic group of representing 4 valencys, R 17The expression carbonatoms is that 1～carbonatoms is the organic group of 90 divalent.)
In addition, as polyimide, preferably comprise the diamines of following general formula (15) expression as two amine components of the polyimide structures that constitutes above-mentioned general formula (3) expression.
General formula (15)
Figure BDA00003375991600351
(in the formula (15), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency, can be the same or different.R 3, R 6, R 9, R 12And R 15The expression carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, and m, n, p are the integer below 30 0 or more independently of one another, satisfied 1 ≦ (m+n+p) ≦ 30.)
As METHODS OF SYNTHESIS OF POLYIMIDE, can enumerate following synthesis method: make the aliphatie diamine polymerization, cyclisation of tetracarboxylic dianhydride and above-mentioned general formula (15) expression and obtain polyimide, make the diamines polymerization of tetracarboxylic dianhydride and following general formula (16) expression then.
General formula (16)
H 2N-R 17-NH 2
(in the formula (16), R 17The expression carbonatoms is that 1～carbonatoms is the organic group of 90 divalent.)
As the tetracarboxylic dianhydride, can enumerate biphenyl-3,3 ', 4,4 '-tetracarboxylic dianhydride (below, abbreviate " BPDA " as), benzophenone-3,3 ', 4,4 '-tetracarboxylic dianhydride (below, abbreviate " BTDA " as), the two O-phthalic acid dianhydrides of oxygen (below, abbreviate " ODPA " as), sulfobenzide-3,3 ', 4,4 '-tetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoesters acid anhydrides) (below, abbreviate " TMEG " as), TOPOT 2,2 (trimellitic acid monoesters acid anhydrides), to biphenylene two (trimellitic acid monoesters acid anhydrides), metaphenylene two (trimellitic acid monoesters acid anhydrides), adjacent phenylene two (trimellitic acid monoesters acid anhydrides), pentanediol two (trimellitic acid monoesters acid anhydrides) (below, abbreviate " 5-BTA " as), decanediol two (trimellitic acid monoesters acid anhydrides), pyromellitic acid dianhydride, two (3,4-dicarboxyl phenyl) ether dicarboxylic anhydride, 4,4 '-(2,2-hexafluoro isopropylidene) two O-phthalic acid dianhydrides, methyl-terphenyl-3,3 ', 4,4 '-tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, dicyclo [2,2,2] suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride, tetramethylene-1,2,3, the 4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentadiene tricarboxylic acid-2,6:3, the 5-dicarboxylic anhydride, 4-(2,5-dioxo tetrahydrofuran (THF)-3-yl)-1,2,3,4-naphthane-1, the 2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, etc.Above-mentioned tetracarboxylic dianhydride may be used alone, can also be 2 or more kinds in combination.Need to prove, from the aspect of the development of polyimide, more preferably BPDA, ODPA, BTDA, TMEG, 5-BTA, decanediol two (trimellitic acid monoesters acid anhydrides).
Diamines as above-mentioned general formula (15) expression, as long as it is then unqualified to have the structure of above-mentioned general formula (15) expression, can enumerate 1,8-diamino-3, polyethyleneoxide diamine compounds such as 6-dioxy base octane, Huntsman society makes JEFFAMINE EDR-148, polyoxyalkylene diamines compounds such as EDR-176, JEFFAMINE D-230, D-400, D-2000, D-4000, the polyetheramine D-230 that BASF society makes, D-400, polypropyleneoxide diamine compounds such as D-2000, HK-511, ED-600, ED-900, ED-2003, XTJ-542 etc. have the compound of different oxyalkylene alkyl etc.By using these compounds with oxyalkylene alkyl, can reduce the warpage of the FPC after polyimide is fired.
In the diamines of above-mentioned general formula (15) expression, m, n, p are the integer below 30 more than 0 independently of one another.From the aspect of insulating reliability, preferred 1 ≦ (m+n+p) ≦ 30, more preferably 3 ≦ (m+n+p) ≦ 10.By inference, as 1 ≦ (m+n+p) ≦ 30, by making the skeleton with oxyalkylene alkyl short, thereby can improve the Young's modulus of polyimide, improve insulating reliability.Infer in addition, usually under the short situation of such oxyalkylene alkyl skeleton, the tendency that can have the warpage of showing, but, in the present embodiment, by share 2 officials energy hydroxy-containing compounds and blocked isocyanate, can under the state that warpage is kept with good state, further improve insulating reliability.
The polyimide of present embodiment has polyimide structures, polyamic acid structure respectively as repeated structural unit, and by import the diamines of above-mentioned general formula (15) expression in polyimide structures, the molecular weight of polyimide varnish and film is stable.If the diamines of above-mentioned general formula (15) is imported the polyamic acid structure, then the alkalescence of aliphatie diamine is high, compares the depolymerization of polyamic acid with existing polyamic acid and is carried out, and the molecular weight reduction becomes remarkable.By importing polyimide structures, can not be subjected to the influence of the alkalescence of aliphatie diamine, the molecular weight stabilization.
Diamines as above-mentioned general formula (16) expression, can enumerate 1, two (4-amino-benzene oxygen) paraffinic hydrocarbonss of 3-, 1, two (4-amino-benzene oxygen) paraffinic hydrocarbonss of 4-, 1, two (4-amino-benzene oxygen) paraffinic hydrocarbonss of 5-, 1, the 4-diaminobenzene, 1, the 3-diaminobenzene, 2, the 4-diaminotoluene, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,7-diamino-dimethyl Dibenzothiophene-5, the 5-dioxide, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 4,4 '-two (4-aminophenyl) thioether, 4,4 '-diaminobenzene anilide, 1, two (the 4-amino-benzene oxygens)-2 of 3-, the 2-dimethylpropane, 1, two [2-(4-amino-benzene oxygen) oxyethyl group] ethane of 2-, 9, two (4-aminophenyl) fluorenes of 9-, 5-amino-1-(4-amino methyl)-1,3,3-trimethylammonium 1, the 2-indane, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-(below, abbreviate APB as), 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-(below, abbreviate BAPP as), trimethylene-two (4-Aminobenzoate) (being designated hereinafter simply as TMAB), 4-aminophenyl-4-Aminobenzoate, 2-methyl-4-aminophenyl-4-Aminobenzoate, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 1-amino-3-amino methyl-3,5, the 5-trimethyl-cyclohexane, 3,3 '-dicarboxyl-4,4 '-diaminodiphenyl-methane, 3, the 5-diaminobenzoic acid, 3,3 '-dihydroxyl-4,4 '-benzidine, 1,3-two (4-amino-benzene oxygen benzene) etc.Wherein, from the low Tg of polyimide, the aspect of development, be preferably APB, BAPP, TMAB.Can also be with these diamines parts as the diamines that in polyimide, uses.
In addition, in the present embodiment, polyimide preferably has the structure of following general formula (6) expression as repeating unit.
General formula (6)
Figure BDA00003375991600371
(in the formula (6), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency, can be the same or different.R 3, R 6, R 9, R 12And R 15The expression carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys.M, n, p represent the integer below 30 more than 0 independently of one another.R 16The organic group of representing 4 valencys, R 17The expression carbonatoms is that 1～carbonatoms is the organic group of 90 divalent.A, B, C represent the mole % of each unit, satisfy 0.10 ≦ (A+B)/(A+B+C) ≦ 0.85.)
In the structure of above-mentioned general formula (6) expression, aspect from development, warpage and insulating reliability, preferred 0.10 ≦ (A+B)/(A+B+C) ≦ 0.85, more preferably 0.15 ≦ (A+B)/(A+B+C) ≦ 0.8, further preferred 0.2 ≦ (A+B)/(A+B+C) ≦ 0.7.Be more than 0.10 by (A+B) as the structure of the diamines that comprises above-mentioned general formula (15) expression with respect to integral body, can reduce warpage.In addition, be below 0.85 by (A+B) as the structure of the diamines that comprises above-mentioned general formula (15) expression with respect to integral body, the reduction of Young's modulus and second-order transition temperature (Tg) is suppressed, and insulating reliability is maintained.In addition, be below 0.85, to show solvability for alkaline-based developer by (A+B) as polyimide structures with respect to integral body, it is good that development becomes.
For the main chain of polyimide is terminal, so long as the structure that performance is not exerted an influence then is not particularly limited.Can be the dicarboxylic anhydride that uses when making polyimide, the end of diamines, can also utilize other acid anhydrides, amine compound etc. with end closure.
As the weight-average molecular weight of polyimide, be preferably more than 1000 below 1000000.Herein, weight-average molecular weight refers to, the polystyrene of known heavy average molecular weight is utilized the molecular weight of gel permeation chromatography as standard.From the aspect of polyimide film strength, weight-average molecular weight is preferably more than 1000.In addition, from the viscosity of the resin combination that contains polyimide, the aspect of formability, be preferably below 1000000.Weight-average molecular weight is more preferably more than 5000 below 500000, is preferably especially more than 10000 below 300000, most preferably is more than 20000 below 50000.
Having polyimide structures and polyamic acid structure respectively can make by following operation as the polyimide of repeating unit: dicarboxylic anhydride and diamines are reacted, the operation (operation 1) at the polyimide position in synthetic the 1st stage with non-equimolar amount; The operation (operation 2) at the polyamic acid position in then synthetic the 2nd stage.Below, each operation is described.
(operation 1)
Operation to the polyimide position in synthetic the 1st stage describes.Operation as the polyimide position of synthesizing for the 1st stage is not particularly limited, and can be suitable for known method.More particularly, utilize following method to obtain.At first, with two amine solvents and/or be scattered in the polymer solvent, add the dicarboxylic anhydride powder therein.Then, add the solvent with the water azeotropic, use mechanical stirrer on one side azeotropic remove the water that by-product is given birth to, on one side heated and stirred 0.5 hour～96 hours, be preferably 0.5 hour～30 hours.This moment, monomer concentration was below the above 95 quality % of 0.5 quality %, was preferably below the above 90 quality % of 1 quality %.
When the synthesis of polyimides position, can obtain the polyimide position by adding known imidization catalyst, also can obtain the polyimide position by the catalyst-free condition.Imidization catalyst is not particularly limited, can enumerates the tertiary amine etc. of the lactone compound, pyridine, quinoline, N-methylmorpholine, triethylamine and so on of the acid anhydrides, γ-Wu Neizhi, gamma-butyrolactone, γ-tetronic acid, γ-phthalide, γ-tonka bean camphor, γ-phthalide acid and so on of diacetyl oxide and so on.In addition, can be the mixture more than a kind or 2 kinds as required.Wherein, particularly from reactive height with to the aspect of the influence of next reaction, mixed system and the catalyst-free condition of preferred especially γ-Wu Neizhi and pyridine.
As the addition of imidization catalyst, if establishing polyamic acid is 100 mass parts, then be preferably below 50 mass parts, more preferably below 30 mass parts.
The reaction solvent that uses during as the synthesis of polyimides position, the carbonatoms that can enumerate dme, diethyl ether, methyl ethyl ether, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and so on are the ether compound below 9 more than 2; The carbonatoms of acetone, methyl ethyl ketone and so on is the ketone compound below 6 more than 2; The carbonatoms of Skellysolve A, pentamethylene, normal hexane, hexanaphthene, methylcyclohexane, naphthane and so on is the saturated hydrocarbon compound below 10 more than 5; The carbonatoms of benzene,toluene,xylene, trimethylbenzene, tetraline and so on is the aromatic hydrocarbon compound below 10 more than 6; The carbonatoms of methyl acetate, ethyl acetate, gamma-butyrolactone, methyl benzoate and so on is the ester cpds below 12 more than 3; Chloroform, methylene dichloride, 1, the halide of the carbonatoms 1～10 of 2-ethylene dichloride and so on; Acetonitrile, N, the carbonatoms of dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-and so on are the nitrogenous compound below 10 more than 2; The sulfocompound of dimethyl sulfoxide (DMSO) and so on.These can be the mixture more than a kind or 2 kinds as required.As particularly preferred solvent, can enumerate carbonatoms is that the ether compound below 9 more than 2, carbonatoms are that the ester cpds below 12 more than 3, carbonatoms are that the aromatic hydrocarbon compound below 10 more than 6, carbonatoms are the nitrogenous compound below 10 more than 2.These can be considered industrial productivity, the influence of next reaction etc. is selected arbitrarily.
In polyimide position synthetic, preferably with temperature of reaction be more than 15 ℃ 250 ℃ with the enforcement of getting off.If temperature of reaction is then initiation reaction more than 15 ℃, and if 250 ℃ with the next inactivation that does not have catalyzer.Be preferably more than 20 ℃ below 220 ℃, more preferably more than 20 ℃ below 200 ℃.
React the needed time according to purpose or reaction conditions and different, be generally in 96 hours, suit especially to implement 30 minutes to 30 hours scope.
(operation 2)
Then, the operation to the polyamic acid position in synthetic the 2nd stage describes.In the polyamic acid position in the 2nd stage synthetic, by the polyimide position that obtains in the operation 1 is used as starting raw material, and append diamines and/or dicarboxylic anhydride and its polymerization is implemented.Polymerization temperature during as the synthesizing polyamides in the 2nd stage acid position is preferably more than 0 ℃ below 250 ℃, more preferably more than 0 ℃ below 100 ℃, is preferably especially more than 0 ℃ below 80 ℃.
The needed time of reaction in synthesizing polyamides when acid is generally in 96 hours according to purpose or reaction conditions and different, suits especially to implement 30 minutes to 30 hours scope.
As reaction solvent, can use with operation 1 in be used for the polyimide position synthetic solvent phase with solvent.Under this situation, can directly use the reaction soln of operation 1 to carry out the synthetic of polyamic acid position.In addition, also can use the solvent different with the synthetic solvent that is used for the polyimide position.
As such solvent, the carbonatoms that can enumerate dme, diethyl ether, methyl ethyl ether, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and so on is the ether compound below 9 more than 2; The carbonatoms of acetone, methyl ethyl ketone and so on is the ketone compound below 6 more than 2; The carbonatoms of Skellysolve A, pentamethylene, normal hexane, hexanaphthene, methylcyclohexane, naphthane and so on is the saturated hydrocarbon compound below 10 more than 5; The carbonatoms of benzene,toluene,xylene, trimethylbenzene, tetraline and so on is the aromatic hydrocarbon compound below 10 more than 6; The carbonatoms of methyl acetate, ethyl acetate, gamma-butyrolactone, methyl benzoate and so on is the ester cpds below 12 more than 3; Chloroform, methylene dichloride, 1, the halide of the carbonatoms 1～10 of 2-ethylene dichloride and so on; Acetonitrile, N, the carbonatoms of dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-and so on are the nitrogenous compound below 10 more than 2; The sulfocompound of dimethyl sulfoxide (DMSO) and so on.
These can be the mixture more than a kind or 2 kinds as required.As particularly preferred solvent, can enumerate carbonatoms is that the ether compound below 9 more than 2, carbonatoms are that the ester cpds below 12 more than 3, carbonatoms are that the aromatic hydrocarbon compound below 10 more than 6, carbonatoms are the nitrogenous compound below 10 more than 2.These can be considered industrial productivity, the influence of next reaction etc. is selected arbitrarily.
The polyimide of making after stopping can directly use with the state that is dissolved in the reaction solvent, also can utilize following method recovery and refining.In addition, the polyimide after manufacturing stops is by removing the solvent underpressure distillation in the reaction soln to reclaim.
As the process for purification of polyimide, can enumerate the method for utilizing filtration under diminished pressure, pressure filtration etc. that the undissolved dicarboxylic anhydride in the reaction soln and diamines are removed.In addition, can be embodied in the poor solvent and to add reaction soln and make that it is separated out, what is called utilize reppd process for purification.Under the situation of the highly purified especially polyimide of these external needs, can also be the process for purification based on the extraction of using supercritical co.
In the photosensitive polymer combination of present embodiment, by containing 2 officials energy hydroxy-containing compounds and blocked isocyanate, can improve insulating reliability, and suppress warpage.By inference, the reaction of the isocyanate group that the hydroxyl that can hydroxy-containing compounds contains by 2 officials and blocked isocyanate contain forms crosslinked body, and the formation by this crosslinked body has improved insulating reliability.In addition, 2 officials can hydroxy-containing compounds enter in the skeleton of polyimide and exist as second composition, and the contraction of the polyimide skeleton in the time of can preventing from solidifying thus can suppress warpage.Think in addition, by comprising blocked isocyanate, can carry out low-temperature curing at low temperatures with the carboxyl inerting, the contraction of the polyimide skeleton in the time of therefore can preventing from solidifying can suppress warpage.
Need to prove, in the above-described embodiment, to using polyimide to be illustrated as the example of (A) macromolecular compound, but, as (A) macromolecular compound, can also use the polyimide that do not comprise the polyamic acid structure, do not comprise the polymeric amide of polyimide structures, comprise polyamidoimide of polyamic acid structure and polyimide structures etc. simultaneously.
In addition, in the resin combination of present embodiment, from stable on heating aspect, the mol ratio of the isocyanate group that the hydroxyl that 2 officials energy hydroxy-containing compounds contains and blocked isocyanate contain is preferably hydroxyl/isocyanate base=0.5～1.
(b) 2 officials can hydroxy-containing compounds
As 2 officials energy hydroxy-containing compounds, in reaching the scope of effect of the present invention, can use the material same with the multifunctional hydroxy-containing compounds that in the resin combination of above-mentioned the 1st embodiment, uses.
(c-1) blocked isocyanate compounds
As blocked isocyanate compounds, can use the material same with the material that in the resin combination of above-mentioned the 1st embodiment, uses.In addition, with the resin combination of the 1st embodiment similarly, in reaching the scope of effect of the present invention, can also use other polyfunctional isocyanate's compound and Duo Guan Neng oxazoline compound.
(D) sensitizer
The photosensitive polymer combination of present embodiment preferably comprise have more than at least 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound as sensitizer, and further comprise (E) Photoepolymerizationinitiater initiater.Sensitizer in the photosensitive polymer combination of present embodiment represents to have the compound of following character, and the structure of described compound changes because of rayed, and the solvability in solvent changes.In the photosensitive polymer combination of present embodiment, by comprise have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound and Photoepolymerizationinitiater initiater, can also utilize have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound form crosslinked body, therefore development property and insulating reliability are improved.
As have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound can enumerate tristane dihydroxymethyl diacrylate, ethylene oxide (EO) modified bisphenol A dimethacrylate, the modified hydrogenated bisphenol a diacrylate of EO, 1,6-hexylene glycol (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, 2-two (to hydroxyphenyl) propane two (methyl) acrylate, three (2-acryloxy ethyl) isocyanuric acid ester, 6-caprolactone modification three (acryloxy ethyl) isocyanuric acid ester, glycerine three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, polyoxyethyl propyl trimethylolpropane tris (methyl) acrylate, polyoxy ethyl trimethylolpropane tris (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, trimethylolpropane tris glycidyl ether (methyl) acrylate, dihydroxyphenyl propane diglycidyl ether two (methyl) acrylate, β-hydroxy propyl-Beta '-(acryloxy)-propyl group phthalic ester, phenoxy group polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three/four (methyl) acrylate etc.Wherein, from development and the aspect of the warpage after firing, be preferably EO modified bisphenol A dimethacrylate, the modified hydrogenated bisphenol a diacrylate of EO, tetramethylolmethane three/four (methyl) acrylate.
In addition, from the aspect of development and insulating reliability, be preferably the compound with 2 two keys and the combination of compounds with two keys more than 3.By inference and since have more than 3 two keys compound formation upright and outspoken crosslinked body, the Young's modulus of cured film and second-order transition temperature (Tg) raise, insulating reliability improves.
Usually comprising under the situation with compound of two keys more than 3, because the cross-linking set increase, thereby have the tendency that warpage takes place.But, in the present embodiment, 2 officials can hydroxy-containing compounds not with the compound formation crosslinking structure with two keys, and in photosensitive polymer combination as the existence of second composition, can alleviate warpage thus.
As the compound with two keys more than 3, can enumerate tetramethylolmethane three/tetraacrylate (trade(brand)name: Aronix (registered trademark) M-306, the synthetic society in East Asia makes), TriMethylolPropane(TMP) PO modification triacrylate (trade(brand)name: Aronix M-310, the synthetic society in East Asia makes), tetramethylol methane tetraacrylate (trade(brand)name: A-TMMT, Xin Zhong village chemical industry society makes), EO modified glycerol three (methyl) acrylate (trade(brand)name: A-GLY-9E (EO modification 9mol), Xin Zhong village chemical industry society makes), ditrimethylolpropane tetraacrylate (trade(brand)name: Aronix M-408, the synthetic society in East Asia makes), Dipentaerythritol five acrylate and dipentaerythritol acrylate (trade(brand)name: Aronix M-403, the synthetic society in East Asia makes) etc.
About having more than 2 the amount of (methyl) acrylic compound that can photopolymerisable unsaturated double-bond, be made as in the amount with polyimide under the situation of 100 mass parts, aspect from development, be preferably below above 60 mass parts of 5 mass parts, more preferably below above 40 mass parts of 10 mass parts.
Need to prove, in the resin combination of present embodiment, under situation about not using as photoresist, may not need to use (D) sensitizer.
(E) Photoepolymerizationinitiater initiater
As Photoepolymerizationinitiater initiater; can enumerate 2; 2-dimethoxy-1; the benzyl dimethyl ketal class of 2-diphenylethane-1-ketone and so on; benzyl dipropyl ketal class; benzyl phenylbenzene ketal class; the benzoin methylether class; ethoxybenzoin; thioxanthone; 2; 4-dimethyl thioxanthone; 2; the 4-diethyl thioxanthone; the 2-isopropyl thioxanthone; the 4-isopropyl thioxanthone; 2; the 4-isopropyl thioxanthone; 2-fluorine thioxanthone; 4-fluorine thioxanthone; the 2-clopenthixal ketone; the 4-clopenthixal ketone; 1-chloro-4-propoxy-thioxanthone; benzophenone; 4; 4 '-two (dimethylamino) benzophenone [tetramethyldiaminobenzophenone]; 4; 4 '-two (diethylamino) benzophenone; 2; 2-dimethoxy-aromatic ketone compounds such as 2-phenyl methyl phenyl ketone; triarylimidazoles dipolymers such as lophine dipolymer; acridine compounds such as 9-phenylacridine; α; alpha, alpha-dimethyl oxygen base-α-morpholino-methylthio phenyl benzoylformaldoxime; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; oxime ester compounds such as N-aryl-a-amino acid; p-(dimethylamino)-benzoic acid; p-(dimethylamino)-benzoic acid; to the diethyl amino yl benzoic acid; to the diisopropylaminoethyl phenylformic acid; parabenzoic acid ester; 1-hydroxyl-cyclohexyl-phenyl-ketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone; 2-hydroxyl-1-4-[(2-hydroxy-2-methyl-propionyl)-benzyl] phenyl }-2-methyl-propane-Alpha-hydroxy alkylbenzene ketones such as 1-ketone; 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone; 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-alpha-aminoalkyl benzophenone classes such as 1-butanone; (2; 4; the 6-trimethylbenzoyl) diphenyl phosphine oxide; phenyl two (2; 4; the 6-trimethylbenzoyl) acylphosphine oxide class such as phosphine oxide; 1,2-acetyl caproyl 1-[4-(thiophenyl)-2-(O-benzoyl oximes)]; ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-oxime ester classes such as (O-ethanoyl oximes) etc.Among these, from the aspect of sensitivity, be preferably oxime ester class.
About the amount of Photoepolymerizationinitiater initiater, be made as in the amount with polyimide under the situation of 100 mass parts, from the aspect of sensitivity and resolving power, be preferably below above 40 mass parts of 0.01 mass parts.More preferably below above 35 mass parts of 0.5 mass parts.
(F) phosphorus compound
Photosensitive polymer combination preferably contains phosphorus compound.Phosphorus compound is so long as comprise the compound that contains phosphorus atom of phosphorus atom in the structure, then unqualified.As such phosphorus compound, can enumerate the phosphate compound with phosphate ester structure or have phosphazene compound of phosphine nitrile structure etc.
As phosphate compound, can enumerate aliphatics organic group that trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, three iso-butyl ester of phosphoric acid, tri-2-ethylhexyl phosphate etc. will comprise aliphatic alkyl as substituent phosphoric acid ester, tricresyl phosphate (butoxyethyl group) ester etc. Sauerstoffatom as substituent phosphoric acid ester, triphenylphosphate, phosphoric acid trimethylbenzene phenolic ester, tricresyl phosphate (dimethylbenzene) ester, Resorcinol two (diphenyl phosphoester) etc. with the aromatic series organic group as substituent phosphate compound etc.Among these, from the aspect of development, be preferably tricresyl phosphate (butoxyethyl group) ester, three iso-butyl ester of phosphoric acid.
As phosphazene compound, can enumerate the structure of following general formula (17), following general formula (18) expression etc.
General formula (17)
General formula (18)
As the R in the phosphazene compound of above-mentioned general formula (17) and above-mentioned general formula (18) expression 21, R 22, R 23, R 24, so long as carbonatoms is that the organic group below 20 is then unqualified more than 1.If carbonatoms is more than 1, then have the tendency of the flame retardant resistance of showing, thereby preferred.If carbonatoms is below 20, then have the tendency compatible with polyimide, thereby preferred.Wherein, from the aspect of performance flame retardant resistance, preferred especially is the functional group of the phenolic compound below 18 more than 6 from carbonatoms.As such functional group, can enumerate functional group, pyridine, imidazoles, triazole, tetrazole ring etc. that functional group, 1-naphthyl, 2-naphthyl that phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-cyano-phenyl, 3-cyano-phenyl, 4-cyano-phenyl etc. have phenyl etc. have a naphthyl from functional group of nitrogen-containing heterocycle compound etc.These compounds can use a kind of as required, also can be with two or more being used in combination.Wherein, owing to the easiness that obtains, preferably has the compound of phenyl, 3-aminomethyl phenyl, 4-hydroxyphenyl, 4-cyano-phenyl.
As long as the v in the phosphazene compound of above-mentioned general formula (17) expression is 25 with next unqualified more than 3.If more than 3, then show flame retardant resistance, if below 25, the solvability height in organic solvent then.Wherein, particularly because the easiness that obtains, thereby to be preferably v be more than 3 below 10.
As long as the w in the phosphazene compound of above-mentioned general formula (18) expression is 10000 with next unqualified more than 3.If more than 3, then show flame retardant resistance, if below 10000, the solvability height in organic solvent then.Wherein, particularly because the easiness that obtains, thereby be preferably more than 3 below 100.
As long as G and J in the phosphazene compound of above-mentioned general formula (18) expression are that carbonatoms is that the organic group below 30 is then unqualified more than 3.Wherein, as G, be preferably-N=P (OC 6H 5) 3,-N=P (OC 6H 5) 2(OC 6H 4OH) ,-N=P (OC 6H 5) (OC 6H 4OH) 2,-N=P (OC 6H 4OH) 3,-N=P (O) (OC 6H 5) ,-N=P (O) (OC 6H 4OH).As J, be preferably-P (OC 6H 5) 4,-P (OC 6H 5) 3(OC 6H 4OH) ,-P (OC 6H 5) 2(OC 6H 4OH) 2,-P (OC 6H 5) (OC 6H 4OH) 3,-P (OC 6H 4OH) 4,-P (O) (OC 6H 5) 2,-P (O) (OC 6H 4OH) 2,-P (O) (OC 6H 5) (OC 6H 4OH) etc.
As phosphorus compound, can use a kind of phosphorus compound, also two or more phosphorus compounds can be used in combination.
About the addition of the phosphorus compound in the photosensitive polymer combination, be made as in the amount with polyimide under the situation of 100 mass parts, from aspects such as developments, be preferably below 50 mass parts.From the aspect of the flame retardant resistance of cured body, more preferably below 45 mass parts.In addition, if more than 5 mass parts, can bring into play effect.
(G) other compounds
In photosensitive polymer combination, its performance not being produced in the dysgenic scope, can comprise other compounds.Specifically, can enumerate the heat-curing resin of the toughness of the film after firing for raising and solvent resistance, thermotolerance (thermostability) and have reactive compound etc. with polyimide.In addition, can enumerate for the heterogeneous ring compound that improves adaptation and be used for the painted pigment of film and dyestuff etc.
As heat-curing resin, can enumerate Resins, epoxy, cyanate ester resin, unsaturated polyester resin, benzoxazine colophony, benzoxazole quinoline, phenol resins, melamine resin, maleimide compound etc.
As having reactive compound with polyimide, can enumerate can with polymkeric substance in carboxyl, amino and terminal anhydride reaction and form compound of three-dimensional crosslinking structure etc.Wherein, preferably by heating amino, the so-called hot generated base alkaline agent compound that produces as alkali.For example, have by with the amino of alkali cpds such as amine with acid such as sulfonic acid make the salt structure, utilize the protection of two carbonate products, utilize chloride compounds to protect resulting compound.Thus, can make the hot generated base alkaline agent that does not at room temperature show alkalescence and stablize, produce by the heating deprotection alkali.
Heterogeneous ring compound is so long as to comprise heteroatomic ring type compound then unqualified.Herein, the heteroatoms in the present embodiment can be enumerated oxygen, sulphur, nitrogen, phosphorus.As concrete example, can enumerate glyoxal ethyline, the 2-undecyl imidazole, 2-ethyl-4-methylimidazole, the imidazoles of 2-phenylimidazole and so on, 1, the N-alkyl substituted imidazole of 2-methylimidazole and so on, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole etc. contains the imidazoles of aromatic group, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-ethyl-4-methylimidazole, 1-cyano ethyl-2-undecyl imidazole, the imidazoles of 1-cyano ethyl-cyano-containings such as 2-phenylimidazole, siliceous imidazolium compoundss such as imidazoles such as imidazoles silane, the 5-Methylbenzotriazole, 1-(1 ', 2 '-dicarboxyl ethyl benzotriazole), 1-triazole compounds such as (2-ethylhexyl amino methyl benzotriazoles), 2-methyl-oxazole compounds such as 5-Ben base benzoxazole etc.
As pigment and dyestuff, can enumerate the phthalocyanine based compound.
As long as the addition of other compounds above 30 mass parts that are 0.01 mass parts are with next unqualified.If more than 0.01 mass parts, then adaptation and tint permanence on film have the tendency of abundant raising, if below 30 mass parts, then photosensitivity etc. are not had detrimentally affect.Photosensitive polymer combination can contain organic solvent arbitrarily.
Organic solvent is so long as can dissolve and/or disperse the material of polyimide then unqualified equably.As such organic solvent, the carbonatoms that can enumerate dme, diethyl ether, methyl ethyl ether, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and so on is the ether compound below 9 more than 2; The carbonatoms of acetone, methyl ethyl ketone and so on is the ketone compound below 6 more than 2; The carbonatoms of Skellysolve A, pentamethylene, normal hexane, hexanaphthene, methylcyclohexane, naphthane and so on is the saturated hydrocarbon compound below 10 more than 5; The carbonatoms of benzene,toluene,xylene, trimethylbenzene, tetraline and so on is the aromatic hydrocarbon compound below 10 more than 6; The carbonatoms of methyl acetate, ethyl acetate, gamma-butyrolactone, methyl benzoate and so on is the ester cpds below 9 more than 3; Chloroform, methylene dichloride, 1, the halide of the carbonatoms 1～10 of 2-ethylene dichloride and so on; Acetonitrile, N, the carbonatoms of dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-and so on are the nitrogenous compound below 10 more than 2; The sulfocompound of dimethyl sulfoxide (DMSO) and so on.
These can be the mixture more than a kind or 2 kinds as required.As particularly preferred solvent, can enumerate carbonatoms and be the ether compound below 9 more than 2, carbonatoms and be the ester cpds below 9 more than 3, carbonatoms and be the aromatic hydrocarbon compound below 10 more than 6, carbonatoms and be the nitrogenous compound below 10 more than 2, and the mixture more than a kind or 2 kinds in them.In addition, from the deliquescent aspect of polyimide, be preferably triethylene glycol dimethyl ether, N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, N, dinethylformamide, N,N-dimethylacetamide.
As the concentration of the polyimide in the resin combination that is constituted by polyimide and organic solvent, then be not particularly limited so long as can form the concentration of resin-formed body.From the aspect of the thickness of the resin-formed body of made, the concentration of polyimide is preferably more than the 1 quality %, and from the inhomogeneity aspect of the thickness of resin-formed body, the concentration of polyimide is preferably below the 90 quality %.From the aspect of the thickness of resulting resin-formed body, more preferably below the above 80 quality % of 2 quality %.
(H) photosensitive film
The photosensitive polymer combination of present embodiment can be suitable for the formation of photosensitive film.The photosensitive film of present embodiment obtains by photosensitive polymer combination is coated on the base material.In addition, in the photosensitive film of present embodiment, preferably possess carrier film and be arranged at the above-mentioned photosensitive polymer combination on this carrier film and be formed at mulch film on this photoresist.
Consider from the aspect of making photosensitive film, as the concentration of the polyimide in the photosensitive polymer combination, be preferably below the above 90 quality % of 1 quality %.As the concentration of polyimide, the aspect from the thickness of photosensitive film is preferably more than the 1 quality %, from the viscosity of photosensitive polymer combination, the inhomogeneity aspect of thickness, is preferably below the 90 quality %.From the aspect of the thickness of resulting photosensitive film, more preferably below the above 80 quality % of 2 quality %.
Then, the manufacture method to photosensitive film describes.At first, photosensitive polymer combination is coated base material.As base material, so long as the base material that does not damage when photosensitive film forms is then unqualified.As such base material, can enumerate silicon wafer, glass, pottery, heat-resistant resin, carrier film etc.As carrier film, can enumerate polyethylene terephthalate film and metallic membrane.Because operation is good, is preferably heat-resistant resin and carrier film, the aspect of the separability after the substrate crimping is preferably the polyethylene terephthalate film especially.
As coating process, can the illustration rod be coated with, roller coat, mould are coated with, scraper plate coating, dip coated, scraper, spraying, flow coat, spin coating, slot coated, bristle coating etc.After the coating, can utilize hot-plate etc. to be called as the heat treated of prebake as required.
Under the situation of making the photosensitive film constituted by photosensitive polymer combination, utilize any means with the solution coat of photosensitive polymer combination to base material (carrier film) arbitrarily.Then, with the photosensitive polymer combination drying and after the dry filmization, form and have for example laminated film of carrier film and photosensitive film.
In addition, also can photosensitive film arrange one deck at least arbitrarily antifouling usefulness or protection usefulness mulch film and make laminated film.In the laminated film of present embodiment, as mulch film, so long as the film of protection such as Low Density Polyethylene photosensitive film is then unqualified.
(I) flexible printed circuit board
The photosensitive film of present embodiment can be suitable for flexible printed circuit board.The flexible printed circuit board of present embodiment possesses: have the base material of distribution and the above-mentioned photosensitive film that arranges in the mode that covers the distribution on this base material.This flexible wiring sheet can obtain by firing after having on the base material of distribution crimping photosensitive film and alkaline development.
As the base material with distribution in the flexible printed circuit board, can enumerate flexible substrate such as the hard substrate of glass epoxy substrate, glass maleimide substrate etc. and so on or coating foil lamination plate etc.Wherein, from the aspect that can bend, be preferably flexible substrate.
For the formation method of flexible printed circuit board, so long as photosensitive film is formed on the base material then unqualified in the mode that covers distribution.As such formation method, can enumerate carry out under the photosensitive film state of contact of the distribution side that makes the base material with distribution and present embodiment that hot pressing, thermosphere are long-pending, the method for thermovacuum compacting, thermovacuum lamination etc. etc.Wherein, from imbed the aspect of photosensitive film to wiring closet, be preferably thermovacuum compacting, thermovacuum lamination.
About the Heating temperature when the layers on substrates with distribution amasss photosensitive film, so long as photosensitive film can be then unqualified with the temperature of base material driving fit.From with aspect and the decomposition of photosensitive film and the aspect of side reaction of the driving fit of base material, be preferably more than 30 ℃ below 400 ℃.More preferably more than 50 ℃ below 150 ℃.
Whole processing to base material with distribution is not particularly limited, and can enumerate salt acid treatment, vitriolization, sodium persulfate aqueous solution processing etc.
Photosensitive film can carry out the photolithography of minus by utilize alkaline development dissolving rayed position part in addition after rayed.Under this situation, be used for light-struck light source and can enumerate high voltage mercury lamp, ultrahigh pressure mercury lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, luminescent lamp, tungsten lamp, argon laser, helium cadmium laser etc.Wherein, be preferably high voltage mercury lamp, ultrahigh pressure mercury lamp.
As the alkaline aqueous solution that is used for developing, so long as it is then unqualified to dissolve the solution of the part beyond the rayed position.As such solution, can enumerate aqueous sodium carbonate, wet chemical, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, tetramethylammonium hydroxide aqueous solution etc.From the aspect of development, be preferably aqueous sodium carbonate and aqueous sodium hydroxide solution.As developing method, can enumerate spray development, immersion development, PADDLE development etc.
Next, by to crimping the printed circuit board (PCB) of photosensitive film fire, form printed circuit board (PCB).From aspect and the aspects such as side reaction and decomposition that solvent is removed, fire preferably and implement with the temperature below 400 ℃ more than 30 ℃.More preferably more than 100 ℃ below 300 ℃.
About the reaction atmosphere in firing, can under air atmosphere, implement, also can under inert gas atmosphere, implement.In the manufacturing of printed circuit board (PCB), above-mentioned to fire the needed time different because of reaction conditions, is generally in 24 hours, suits especially to implement in 1 hour to 8 hours scope.
Warpage after the polyimide of present embodiment and the curing of photosensitive polymer combination is good; and development is also good; when forming cured body, demonstrate chemical proofing, thereby can be used for printed circuit board (PCB) that electronic applications uses and the protective layer formation of circuit substrate in the operating panel of various electronicss etc.; the insulation layer of laminated substrate forms; the silicon wafer that uses in the semiconductor device; semi-conductor chip; the parts of semiconductor device periphery; substrate for mounting semiconductor; heat liberation board; pin; film on the protection of semi-conductor self etc. and insulation and the bonding middle electronic unit that uses forms purposes.Like this, will be called tectum to the protective membrane that the distribution that silicon wafer, coating foil lamination plate, printed circuit board (PCB) etc. upward form is protected.
In addition, the polyimide of present embodiment and photosensitive polymer combination can be suitable for the tectum that flexible printing wiring circuit (FPC) is used with substrate, used for solar batteries substrate, particularly flexible printing wiring circuit with substrate, Electronic Paper with substrate, organic electroluminescent (EL) display screen with the electrical insulating film in base material, the various electron device and liquid crystal display in conjunction with (TAB) automatically with substrate, winding.
(the 3rd embodiment)
The material that uses in the manufacturing process as flexible printed board, proposed to comprise the resin combination of the polyimide with the polyamic acid structure that has the siloxanes position and polyimide structures, described siloxanes position has used silicone diamine as two amine components.In these resin combinations, the siloxanes position exists only in the polyamic acid structure.Therefore, have following problem: polyimide structures is shunk and the generation warpage during curing, and the reduction of the molecular weight of polyamic acid structure simultaneously is remarkable, and it is unstable that the development time of dry film (resin molding) becomes.In addition, in recent years, as the parts installation reliability of flexible printed board, carried out high acceleration stress test (HAST), the material that requires to have the high insulating reliability of HAST patience and suppressed warpage for improving connection reliability.
As (A) macromolecular compound, the inventor is conceived to use has the polyimide structures that there is the siloxanes position and polyamic acid structure as the polyimide this point of structural unit.And find, utilization contain as (A) macromolecular compound have the polyimide structures that there is the siloxanes position and polyamic acid structure as (methyl) acrylic compound with ad hoc structure of the polyimide of structural unit, conduct (D) sensitizer and (E) photosensitive polymer combination of Photoepolymerizationinitiater initiater, can realize having the photosensitive polymer combination of the HAST patience of excellence.
In this photosensitive polymer combination, in polyimide structures, comprise the siloxanes position, thereby can suppress the reduction of the molecular weight of polyamic acid structure, therefore can suppress the reduction of development property.In addition, give the flexibility of appropriateness to the polyimide position of molecular chain, so can reduce the warpage of the resin molding when solidifying.In addition, can hydroxy-containing compounds and blocked isocyanate compounds by comprising 2 officials, can suppress to exist contraction and the segregation of the polyimide at silicone position, the warpage during curing reduces and thermotolerance improves, and the while can be suppressed the reduction with the cementability of base material.Below, the 3rd embodiment of the present invention is specifically described.
The photosensitive polymer combination of the 3rd embodiment of the present invention contain (a) have polyimide structures and polyamic acid structure as polyimide, (D) of structural unit have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound and (E) Photoepolymerizationinitiater initiater.Below, each constitutive requirements is elaborated.
(a) polyimide
The polyimide of present embodiment is to have the polyamic acid structure of the polyimide structures of following general formula (7) expression and following general formula (8) expression respectively as the segmented copolymer of repeated structural unit.The polyimide of present embodiment uses dicarboxylic anhydride and diamines to synthesize.
General formula (7)
Figure BDA00003375991600491
General formula (8)
Figure BDA00003375991600501
(in formula (7) and the formula (8), Z 3, Z 4Be the organic group from the tetracarboxylic dianhydride's of following general formula (9) expression 4 valencys, can be identical separately also can be different.R 18The expression carbonatoms is that 1～carbonatoms is the organic group of 30 divalent, R 19The expression carbonatoms is that 1～carbonatoms is the organic group of 30 1 valency, and e represents the integer below 20 more than 1.)
General formula (9)
In the present embodiment, polyimide comprises the polyimide structures of above-mentioned general formula (7) expression, thereby contains the siloxanes position in the polyimide structures.Thus, the polyimide position of molecular chain is endowed the flexibility of appropriateness, therefore can reduce the warpage of the film after firing.In addition, because polyimide comprises the polyamic acid structure of above-mentioned general formula (8) expression, thereby imported aromatic nucleus in the molecular chain.Thus, can suppress the reduction of the molecular weight of polyamic acid structure, so the development time of the storage stability of photosensitive polymer combination and dry film stability improves.In addition, the polyamic acid structure of polyimide and polyimide structures comprise the organic group from the tetracarboxylic dianhydride's of above-mentioned general formula (9) expression 4 valencys, so molecular chain is endowed the rigidity of appropriateness, thermotolerance raising, insulating reliability (HAST patience) raising.
As the dicarboxylic anhydride that is used for present embodiment, can enumerate pyromellitic acid dianhydride (below, also abbreviate " PMDA " as), the two O-phthalic acid dianhydrides of oxygen (below, also abbreviate " ODPA " as), biphenyl tetracarboxylic dianhydride (below, also abbreviate " BPDA " as).About the two O-phthalic acid dianhydrides of oxygen, biphenyl tetracarboxylic dianhydride, there is constitutional isomer, its structure is not particularly limited.In addition, these dicarboxylic anhydrides can use separately, also can share two or more.
As the aromatic diamine that is used for present embodiment, can enumerate two (3-amino-benzene oxygen) benzene, 1 of 1,3-, two (3-amino-benzene oxygen) benzene, 1 of 4-, two (4-amino-benzene oxygen) benzene of 4-.From the aspect of warpage, be preferably and have 1 of bendability, two (3-amino-benzene oxygen) benzene of 3-.
In addition, as the silicone diamine that is used for present embodiment, so long as the structure of following general formula (19) expression then is not particularly limited.
General formula (19)
Figure BDA00003375991600511
In above-mentioned general formula (7) and the above-mentioned general formula (19), e is for satisfying the integer of 1 ≦ e ≦ 20.If e is below 20, then alkali-soluble and HAST patience are good.As the e in the above-mentioned general formula (19), from the Tg of the polyimide that generates and the aspect of flame retardant resistance, be preferably more than 1 below 15, more preferably more than 1 below 12.
In above-mentioned general formula (7) and the above-mentioned general formula (19), R 18So long as that carbonatoms is the organic group of the divalent below 30 more than 1 is then unqualified.Be the organic group (R of the divalent below 30 more than 1 as carbonatoms 19), the aspect from flame retardant resistance is preferably CH 2, C 2H 4, C 3H 6, C 4H 8Is the organic group of the divalent of the sturated aliphatic hydrocarbon below 10 Deng expression from carbonatoms.
In above-mentioned general formula (7) and the above-mentioned general formula (19), R 19The expression carbonatoms is the organic group below 30 1 or more, can be separately identical also can difference.Be the organic group (R below 30 more than 1 as carbonatoms 19), can enumerate sturated aliphatic hydrocarbon base, unsaturated aliphatic hydrocarbon base, comprise the organic group of ring texture and group that they are combined etc.
As above-mentioned sturated aliphatic hydrocarbon base, can enumerate uncle's alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl; Sechy-drocarbyl such as isobutyl-, isopentyl; Tertiary hydrocarbon bases such as the tertiary butyl etc.
As above-mentioned unsaturated aliphatic hydrocarbon base, can enumerate the double bond containing alkyl of bags such as vinyl, allyl group, ethynyl etc. and comprise alkyl of triple bond etc.
As the above-mentioned functional group that comprises ring texture, can enumerate monocyclic functional groups such as cyclobutyl, cyclopentyl, cyclohexyl, ring decyl, ring octyl group; Polycycle such as norcamphyl, adamantyl functional group; Hetero ring type functional group with pyrroles, furans, thiophene, imidazoles, oxazole, thiazole, tetrahydrofuran (THF), dioxane structure; Comprise the aromatic hydrocarbyl of phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring structure etc.
Be the organic group (R below 30 more than 1 as carbonatoms 19), can comprise halogen atom, heteroatoms and atoms metal.As halogen atom, can enumerate fluorine, chlorine, bromine, iodine.In addition, as heteroatoms, can enumerate oxygen, sulphur, nitrogen, phosphorus.In addition, as atoms metal, can enumerate silicon and titanium.
In addition, be the organic group (R below 30 more than 1 at carbonatoms 19) comprise under the situation of heteroatoms and/or atoms metal R 19Can with heteroatoms and/or the atoms metal Direct Bonding of institute's bonding, also can be situated between by heteroatoms and/or atoms metal bonding.
R as above-mentioned general formula (7) and above-mentioned general formula (19) 19Carbonatoms, consider flame retardant resistance, be preferably more than 1 below 20.In addition, the aspect from the solvent solubility of the polyimide that generates as carbonatoms, is preferably 1～10 especially.
About the compound of above-mentioned general formula (19) expression, as with R 18: propenyl, R 19: the compound that methyl is represented, can enumerate that chemical industry society of SHIN-ETSU HANTOTAI makes
Figure BDA00003375991600521
Toray Dow Corning society makes
Figure BDA00003375991600522
And
Figure BDA00003375991600523
In addition, as with R 18: propenyl, R 19: the compound that phenyl is represented, can enumerate that chemical industry society of SHIN-ETSU HANTOTAI makes
Figure BDA00003375991600524
The main chain of polyimide terminal so long as not the structure that performance is exerted an influence then be not particularly limited.Can be the dicarboxylic anhydride that uses when making polyimide, the main chain end of diamines, also can utilize other acid anhydrides, amine compound etc. with the main chain end closure.
The weight-average molecular weight of polyimide is preferably more than 1000 below 1000000.Herein, weight-average molecular weight refers to that polystyrene with the known heavy average molecular weight as standard, utilizes the molecular weight of gel permeation chromatography.From the aspect of polyimide film strength, weight-average molecular weight is preferably more than 1000.From the viscosity of the resin combination that contains polyimide, the aspect of formability, be preferably below 1000000 in addition.Weight-average molecular weight is more preferably more than 5000 below 500000, is preferably especially more than 10000 below 300000, most preferably is more than 25000 below 50000.
Have respectively in polyimide structures and the manufacture method of polyamic acid structure as the polyimide of repeating unit, can use the manufacture method shown in above-mentioned the 2nd embodiment.
Need to prove, in the above-described embodiment, to having used polyimide (described polyimide has the polyimide structures that there is the siloxanes position and polyamic acid structure as structural unit) to be illustrated as the resin combination of the 2nd mode of (A) macromolecular compound, but, also can be by in reaching the scope of effect of the present invention, using the polyimide that does not comprise the polyamic acid structure in fact, the resin combination that is used as above-mentioned the 1st mode uses.
(b) 2 officials can hydroxy-containing compounds
In the photosensitive polymer combination of present embodiment, preferably containing 2 officials can hydroxy-containing compounds and blocked isocyanate compounds.This is because 2 officials can hydroxy-containing compounds have direct bonding with polyimide, so do not enter in the skeleton and exist as second composition.Thus, the contraction of the polyimide skeleton in the time of can preventing from solidifying can suppress warpage.In addition, by comprising blocked isocyanate compounds, can make the carboxyl inerting of polyimide at low temperatures, can carry out low-temperature curing, the contraction of the polyimide skeleton in the time of therefore can preventing from solidifying can suppress warpage.
In addition, in the photosensitive polymer combination of present embodiment, from stable on heating aspect, the mol ratio of the isocyanate group that the hydroxyl that 2 officials energy hydroxy-containing compounds contains and blocked isocyanate contain is preferably hydroxyl/isocyanate base=0.5～1.
Can hydroxy-containing compounds as 2 officials, can use the identical material of material that uses in the resin combination with above-mentioned the 1st embodiment.Need to prove, as 2 officials energy hydroxy-containing compounds, can also in reaching the scope of effect of the present invention, use the multifunctional hydroxy-containing compounds that contains 2 above hydroxyls.
In the present embodiment, consider from the aspect of taking into account warpage reduction, solder heat resistance and chemical proofing, 2 officials can preferably be contained 1 mass parts～70 mass parts with respect to resin combination 100 mass parts by hydroxy-containing compounds, more preferably contain 1 mass parts～60 mass parts.
(c-1) blocked isocyanate compounds
As blocked isocyanate compounds, can use the material same with the material that in the resin combination of above-mentioned the 1st embodiment, uses.Need to prove, in the present embodiment, as (C) multifunctional cross-linked compound, the example that has used blocked isocyanate compounds is illustrated, but in reaching the scope of effect of the present invention, can also uses polyfunctional isocyanate's compound with 2 above isocyanate group, have multifunctional cross-linked compound, the Duo Guan Neng oxazoline compound of 2 above bridging property functional groups.
(d) (methyl) acrylic compound
As have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound, can enumerate tristane dihydroxymethyl diacrylate, ethylene oxide (EO) modified bisphenol A dimethacrylate, the modified hydrogenated bisphenol a diacrylate of EO, 1,6-hexylene glycol (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, 2-two (to hydroxyphenyl) propane two (methyl) acrylate, three (2-acryloxy ethyl) isocyanuric acid ester, 6-caprolactone modification three (acryloxy ethyl) isocyanuric acid ester, glycerine three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, polyoxyethylene trimethylolpropane tris (methyl) acrylate, polyoxypropylene trimethylolpropane tris (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, trimethylolpropane tris glycidyl ether (methyl) acrylate, dihydroxyphenyl propane diglycidyl ether two (methyl) acrylate, beta-hydroxy propyl group-β '-(acryloxy)-propyl group phthalic ester, phenoxy group polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three/four (methyl) acrylate etc.
In the photosensitive polymer combination of present embodiment, contain have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound.From the aspect of resolving power and HAST patience, preferably comprise (methyl) acrylic compound with two keys more than 3.
As (methyl) acrylic compound with two keys more than 3, (the synthetic society in East Asia makes can to enumerate tetramethylolmethane three/tetraacrylate, Aronix M-306), (Xin Zhong village chemical industry society makes tetramethylol methane tetraacrylate, A-TMMT), (Xin Zhong village chemical industry society makes EO modified glycerol three (methyl) acrylate, A-GLY-9E (EO modification 9mol)), (the synthetic society in East Asia makes the ditrimethylolpropane tetraacrylate, Aronix M-408), (the synthetic society in East Asia makes for Dipentaerythritol five acrylate and dipentaerythritol acrylate, Aronix M-403) etc.
In addition, in the present embodiment, as (methyl) acrylic compound with two keys more than 3, from the aspect of insulating resistance value (HAST patience) and warpage, the compound of following general formula (10) expression more preferably.This be because, the compound of following general formula (10) expression does not enter in the skeleton of polyimide and forms crosslinked body as second composition, the contraction of the polyimide skeleton in the time of can preventing from solidifying thus can suppress warpage.In addition, by inference, owing to do not have the functional group of reduction electrical insulating properties such as hydroxyl, thereby in the polyimide matrix of present embodiment, form upright and outspoken crosslinked body, Tg and the Young's modulus of cured film uprise, and HAST patience improves.
General formula (10)
Figure BDA00003375991600541
(in the formula (10), R 20Expression hydrogen atom or methyl.A plurality of E represent that independently of one another carbonatoms is that 2～carbonatoms is 5 alkylidene group, can be separately identical also can be different.F is 1～10 integer.)
In the above-mentioned formula (10), be that 2～carbonatoms is 6 alkylidene group (E) as carbonatoms, for example, can enumerate vinyl, propenyl, pseudoallyl, butenyl, isobutenyl, pentadienyl, neo-pentyl etc.From the aspect of resolving power, as E, 2 or 3 alkylidene group more preferably.In addition, in the above-mentioned formula (10), from the aspect of flame retardant resistance, as f, be preferably 1～5 especially.
As the compound of above-mentioned general formula (10) expression, can enumerate SR502 (E: vinyl, f:3), SR9035 (E: vinyl, f:5) etc. that Aronix M-350 (E: vinyl, f:1), M-360 (E: vinyl, f:2), M-310 (E: propenyl, f:1), M-321 (E: propenyl, f:2), SARTOMER society that the synthetic society in East Asia makes make.These can use separately, also can share two or more.
In addition, in the photosensitive polymer combination of present embodiment, the warpage after fire and the aspect of resolving power are preferably share (methyl) acrylic compound with 2 two keys and are had (methyl) acrylic compound of two keys more than 3.
As (methyl) acrylic compound with 2 two keys, fragrant family two (methyl) acrylate that is divided into fatty family two (methyl) acrylate and has the bis-phenol structure.As fatty family two (methyl) acrylate, can enumerate polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, polyoxyethylene glycol polypropylene glycol two (methyl) acrylate etc.Specifically, from suppressing the aspect of warpage, preferred nine glycol diacrylates (manufacturing of Xin Zhong village chemical industry society, 9G), seven propylene glycol dimethacrylates (manufacturing of Xin Zhong village chemical industry society, 9PG) etc.
In addition, as fragrant family two (methyl) acrylate, can enumerate the compound of following general formula (20) expression.
General formula (20)
Figure BDA00003375991600551
(in the formula (20), R 25And R 26Expression hydrogen atom or methyl.A plurality of E represent that independently of one another carbonatoms is that 2～carbonatoms is 6 alkylidene group, can be separately identical also can be different.)
In the above-mentioned general formula (20), be that 2～carbonatoms is 6 alkylidene group (E) as carbonatoms, for example, can enumerate vinyl, propenyl, pseudoallyl, butenyl, isobutenyl, pentadienyl, neo-pentyl etc.
In the above-mentioned general formula (20), l and k are respectively 1～10 integer, 2 ≦ l+k ≦ 20.If l and k are respectively below 10, then flame retardant resistance and HAST patience improve.In addition from the aspect of warpage and resolving power, as l and the k in the general formula (20), more preferably be respectively more than 3 below 6,6 ≦ l+k ≦ 12.
As the concrete example in the above-mentioned general formula (20), can enumerate the Aronix M-208 (R that the synthetic society in East Asia makes 25, R 26: hydrogen atom, E: vinyl,
Figure BDA00003375991600553
BPE-500 (the R that Xin Zhong village chemical industry society makes 25, R 26: methyl, E: vinyl, l+k=10), BPE-900 (R 25, R 26: methyl, E: vinyl, l+k=17), A-BPE-500 (R 25, R 26: hydrogen atom, E: vinyl, l+k=10), A-B1206PE (following general formula (21), R 25: hydrogen atom, R 26: methyl, E 1: vinyl, E 2: propenyl, l1+k1=6, l2+k2=12) etc.
General formula (21)
Figure BDA00003375991600552
As the amount that has more than 2 (methyl) acrylic compound that can photopolymerisable unsaturated double-bond, be made as in the amount with polyimide under the situation of 100 mass parts, aspect from resolving power, be preferably below above 60 mass parts of 5 mass parts, more preferably below above 40 mass parts of 10 mass parts.
Need to prove, in the resin combination of present embodiment, be not used as under the situation of photoresist, may not contain (methyl) acrylic compound as (D) sensitizer.
(E) Photoepolymerizationinitiater initiater
As Photoepolymerizationinitiater initiater, can use the material same with the material shown in above-mentioned the 2nd embodiment.
(F) phosphorus compound
As phosphorus compound, can use the material same with the material shown in above-mentioned the 2nd embodiment.In addition, as the phosphazene compound shown in the above-mentioned general formula (17), specifically, can enumerate Rabitle (registered trademark) FP-300, FP-390, (volt sees that society of pharmacy institute makes, is called for short FP-300 (R 21=R 22=4-cyano-phenyl), be called for short FP-390 (R 21=R 22=3-aminomethyl phenyl).
(G) other compounds
In addition, in the photosensitive polymer combination of present embodiment, can comprise other compounds in the dysgenic scope its performance not being caused.As other compounds, can enumerate the material same with the material shown in above-mentioned the 2nd embodiment.
(H) photosensitive film
In addition, the photosensitive polymer combination of present embodiment can similarly be used for the formation of photosensitive film with the photosensitive polymer combination of above-mentioned the 2nd embodiment.
(I) flexible printed circuit board
In addition, the photosensitive polymer combination of present embodiment can similarly be suitable for flexible printed circuit board with the photosensitive polymer combination of above-mentioned the 2nd embodiment.
(the 4th embodiment)
The material that uses in the manufacturing as flexible printed board, proposed whole polyamic acid imidizations are contained comprise hydroxyl and/or carboxyl, alkaline aqueous solution is solvable and the resin combination of the solvable polyimide of solvent.In this resin combination, the laser via processing that need not use in the manufacturing of flexible printed circuit board can be used as the interlayer dielectic that carries out with alkaline aqueous solution and solvent by processing.But, because the solvent that uses in the manufacturing process to flexible printed circuit board and alkaline aqueous solution lack patience, therefore require to improve.And, under the situation that the insulating material lamination of the film form after utilizing the heating and pressurizing pressing with desolventizing is used in wiring board and as interlayer dielectric, owing to be macromolecular compound, thereby the shortage Resin Flow, lack the through hole imbedibility, expectation improves.
The inventor is conceived to use the solvable polyimide of the solvent with hydroxyl and/or carboxyl and siloxanes position as (A) macromolecular compound this point.And, the inventor finds, by comprising the solvent soluble polyimide as (A) macromolecular compound, the 2 officials energy hydroxy-containing compounds of the multifunctional hydroxy-containing compounds of conduct (B) and the oxazoline compound of conduct (C) multifunctional cross-linked compound, can realize the soluble resin combination of following alkali, described resin combination can utilize solvent and alkaline aqueous solution to process before crosslinking reaction, demonstrate good through hole imbedibility, after crosslinking reaction, solvent and alkaline aqueous solution are had excellent patience.Below, the 4th embodiment of the present invention is specifically described.
The resin combination of the 4th embodiment of the present invention contains polyimide that (a) have hydroxyl and/or carboxyl, (b) 2 officials can hydroxy-containing compounds and (c-2) oxazoline compound, with respect to polyimide 100 mass parts, the content of 2 officials energy hydroxy-containing compounds and oxazoline compound is 2 mass parts to 45 mass parts.
In this resin combination, polyimide has hydroxyl and/or carboxyl, 2 officials can hydroxy-containing compounds and the content of oxazoline compound in pre-determined range, through hole imbedibility excellence before crosslinked thus, dissolve in the alkaline aqueous solution, after crosslinked, be insoluble to alkaline aqueous solution.In addition, polyimide has hydroxyl and/or carboxyl, and Yu oxazoline compound reaction thus can suppress warpage.In addition, 2 officials can hydroxy-containing compounds enter in the skeleton of polyimide and exist as second composition, and the contraction of the polyimide skeleton in the time of can preventing from solidifying thus can suppress warpage.In addition, because therefore Bao Han oxazoline compound makes the carboxyl inerting at low temperatures, can carry out low-temperature curing, the contraction of the polyimide skeleton in the time of therefore can preventing from solidifying can suppress warpage.
In this resin combination, polyimide has hydroxyl and/or carboxyl, dissolves in the alkaline aqueous solution thus before curing, is insoluble to alkaline aqueous solution after curing, and shows high heat resistance (for example, high solder heat resistance).In addition, by said structure, the warpage in the time of can suppressing to solidify.
In addition, have hydroxyl and/or carboxyl in the structure of polyimide, but have 2 officials energy hydroxy-containing compounds, the contraction of the polyimide skeleton in the time of can preventing from solidifying in the resin combination by making.That is, 2 officials can hydroxy-containing compounds enter in the skeleton and contain as second composition, can further reduce the warpage of the cured article that is obtained by resin combination thus.In addition, by Han You oxazoline compound, utilize high molecular that the reaction with hydroxyl produces, be cross-linked to form, can be implemented in the insoluble and higher thermotolerance in the alkaline aqueous solution.
In addition, the content of 2 officials energy hydroxy-containing compounds and oxazoline compound is 2 mass parts to 45 mass parts with respect to polyimide 100 mass parts, and polyimide is excessive for other compositions.By this formation, supposition utilizes following mechanism and shows thermotolerance.Oxazolinyl and hydroxyl reaction and form the structure that comprises C=O base, NH base advance and the hydroxyl and/or the carboxylic acid reaction that contain in the remaining polyimide after oxazolinyl and the imidization reaction, form the amide structure that comprises C=O base, NH base and urea structure etc.That is, think by thermofixation form chemically crosslinked between polyimide and the oxazoline compound and 2 officials can hydroxy-containing compounds and the oxazoline compound between chemically crosslinked.Like this, two or more be cross-linked to form three-dimensional cross-linkedly by utilizing, make the polyimide of excellent heat resistance further excessive, further show thermotolerance thus.
The details of each composition that constitutes resin combination then, is described.
(a) polyimide
The polyimide that uses in the resin combination of present embodiment has hydroxyl and/or carboxyl as structural unit.Bridging property functional group reactions by so making polyimide structures part and multifunctional cross-linked compound also solidifies, thereby demonstrates insoluble in the alkaline aqueous solution after curing.In addition, the reaction of remaining carboxyl utilization and oxazoline compound and/or blocked isocyanate compounds and inerting was led to oxazoline compound and/or blocked isocyanate compounds and 2 officials and can be suppressed warpage by hydroxy-containing compounds when making low-temperature curing.
The polyimide that uses in the resin combination of present embodiment has hydroxyl and/or carboxyl as structural unit.Have the diamines of hydroxyl and/or carboxyl by use, hydroxyl and/or carboxyl can be imported in the polyimide.As such diamines, can enumerate 2,5-diaminophenol, 3,5-diaminophenol, 4,4 '-(3,3 '-dihydroxyl) benzidine, 4,4 '-(2,2 '-dihydroxyl) benzidine, 2,2 '-two (3-amino-4-hydroxyphenyl) HFC-236fa, 3-hydroxyl-4-phenylaniline (HAB), 4,4 '-(3,3 '-dicarboxyl) diphenylamine, methylene-bis benzaminic acid (MBAA), 2,5-diaminobenzoic acid (DABA), 3,3 '-dicarboxyl-4,4 '-diamino-diphenyl ether etc.
About other formations of polyimide, can use the formation same with above-mentioned the 1st embodiment.Need to prove, in the above-described embodiment, use is had the solvable polyimide of the solvent at hydroxyl and/or carboxyl and siloxanes position be illustrated as the resin combination of the 2nd mode of (A) macromolecular compound, but also can use by the resin combination that in reaching the scope of effect of the present invention, uses the polyimide that does not comprise the polyamic acid structure in fact be used as above-mentioned the 1st mode.
As the manufacture method of the polyimide of present embodiment, can use the method identical with the manufacture method of the polyimide shown in above-mentioned the 1st embodiment.
(b) 2 officials can hydroxy-containing compounds
The 2 officials energy hydroxy-containing compounds that uses in the resin combination of present embodiment refers to comprise with respect to a molecular chain material of 2 hydroxyls.Can enumerate the material Zai of alkyl such as comprising aliphatics, aromatic series, alicyclic radical in the skeleton Yu under the situation of oxazoline compound crosslink, consider from the aspect that improves insulativity, the material that preferably in skeleton, has the structure of following formula (14) expression, comprise aliphatic compound from suppressing the aspect consideration of warpage, being preferably.This is because by having aliphatic skeleton, can suppress water absorbability and do not damage the effect that suppresses warpage, even also can show high-insulativity when moisture absorption.Need to prove that the effect that suppresses warpage under the situation of the aliphatic group that comprises long-chain improves, thereby preferred.
General formula (14)
Figure BDA00003375991600591
(in the formula (14), X represents aromatic series, Y represent carbonatoms be 1 to carbonatoms be 10 aliphatics, Z represents to be selected from the functional group in ether, ester group, carbonate group, carbamate groups, the urea groups, the integer of h=0～2, the integer of i=0～1, the integer of j=1～1000.)
In addition, for Yu oxazoline compound crosslink, the terminal compound of preferred polyphenol.In addition, particularly in the electronic material purposes, preferably do not comprise the material of halogens such as fluorine and chlorine.
As the concrete example of 2 officials energy hydroxy-containing compounds, can enumerate the polytetramethylene glycol such as PTMG1000 that Mitsubishi Chemical society makes, the polybutadiene diol such as G-1000 that Japan Cao Da society makes, hydrogenated butadiene polymer glycol such as GI-1000, the DURANOL T5651 that chemistry society of Asahi Chemical Industry makes, DURANOL T5652, the polycarbonate diols such as PRAXCELL CD that DURANOL T4671 and Daicel Chemical society make, the polycaprolactone glycols such as PRAXCELL200 that Daicel Chemical society makes, bisphenols such as dihydroxyphenyl propane, the A Hydrogenated Bisphenol A classes such as Rikabinol HB that new Japanese physics and chemistry society makes, chemistry society of SHIN-ETSU HANTOTAI makes X-22-1821, Dow Corning society makes BY16-752, two terminal phenol-modified silicone such as BY16-799 etc.
Among these, consider from the aspect that improves insulativity, be preferably two terminal phenol-modified silicone, polybutadiene diol, hydrogenated butadiene polymer glycol, polycarbonate diol, consider from the aspect that reduces warpage, be preferably two terminal phenol-modified silicone, polycarbonate diol.
In addition, consider aspect reducing warpage and deliquescent organic solvent that 2 officials can hydroxy-containing compounds be preferably and at room temperature be liquid material.In number-average molecular weight, be preferably 500～3000 material, special preferred number average molecular weight is 500～2000 material.
Consider that from the aspect of taking into account warpage reduction, solder heat resistance and chemical proofing 2 officials can preferably be contained 3 mass parts～70 mass parts with respect to resin combination 100 mass parts by hydroxy-containing compounds, more preferably contain 5 mass parts～60 mass parts.
Need to prove, in the present embodiment, as (B) multifunctional hydroxy-containing compounds, 2 officials of containing 2 hydroxyls can hydroxy-containing compounds be illustrated, but in reaching the scope of effect of the present invention, can also use the polyvalent alcohol that contains 2 above hydroxyls etc.
() oxazoline compound c-2
Shi Yong De oxazoline compound refers to that intramolecularly has the compound of 2 Yi Shang oxazolinyls in the resin combination of present embodiment.Make to be the oxazoline compound, preferably and polyimide (macromolecular compound) and/or 2 officials form between can hydroxy-containing compounds when crosslinked, in this is crosslinked, have the material of 2 C=O bases and/or NH base at least.
The concrete example of Zuo Wei oxazoline compound, can enumerate 1,3-two (4,5-dihydro-2-oxazolyl) K-2010E, the K-2020E, the K-2030E, 2 that make of benzene, Japanese catalyst society, two (4-sec.-propyl-2-oxazoline-2-yl) pyridines, 2 of 6-, two (4-phenyl-2-oxazoline-2-yl) pyridines, 2,2 of 6-' isopropylidene two (4-phenyl-2-oxazoline), 2,2 ' isopropylidene two (the 4-tertiary butyl-2-oxazoline) etc.Zhe Xie oxazoline compound can use separately, also can be used in combination of two or more.
Can obtain cured article by heating above-mentioned resin combination.Mode to heating is not particularly limited, in order to dissolve in the alkaline aqueous solution, preferably 50 ℃～140 ℃ heating 1 minute～60 minutes.The main crosslinking reaction that takes place is insoluble to alkaline aqueous solution under the heating of high-temperature area (for example 160 ℃～200 ℃) more.
In above-mentioned high-temperature area, also depend on the thickness of formed resin combination film, utilizing baking oven or hot-plate to make top temperature is 150 ℃～220 ℃ scope, heating is 5 minutes～100 minutes under inert atmospheres such as air or nitrogen, carries out crosslinked thus.Heating temperature can be constant in the time in entire treatment, also can heat up at leisure.The resin combination film can utilize known silk screen printing or precise glue dispensing method in flexible printed circuit substrate and semiconductor wafer surface printing and form.
Resin combination demonstrates excellent thermotolerance by thermofixation; therefore useful as the surface protection film of the surface cure film of semiconductor element, interlayer dielectric, bonding sheet, use in printed circuit board protection insulating film, tellite and interlayer dielectric etc., be applicable to various electronic units.For example, by going up the coating resin composition at Copper Foil F2-WS (12 μ m) and 95 ℃ of dryings 12 minutes, the thickness that can make insulation layer was the Copper Foil of the tape tree fat of 15 μ m.Tellite as flexibility, use ESPANEX M (chemistry society of Nippon Steel makes) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)), utilize vacuum pressing with 100 ℃, 1 minute, the Copper Foil of 4MPa lamination tape tree fat at this circuit substrate, form the photosensitivity resist layer and with alkaline aqueous solution dissolving resist layer and resin combination and after forming through hole at Copper Foil, peel off resist, solidified 1 hour at 180 ℃, obtain interlayer dielectric thus.So the interlayer dielectric that forms can be brought into play the good insulation performance characteristic.Need to prove that the thermofixation of the resin combination in the present embodiment is carried out under lower temperature condition (for example 160 ℃～200 ℃), therefore the oxidation that does not produce copper.
In addition; use the two sides copper foil laminate of ESPANEX M (chemistry society of Nippon Steel makes) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)); make two face component circuit substrate is installed; at this circuit substrate coating resin composition and dry; utilize alkaline aqueous solution processing after fixing; resin combination is used as surface protection film, also can bring into play the good insulation performance characteristic.Herein, the thickness of surface protection film is preferably 1 μ m～50 μ m.This be because, be more than the 1 μ m by making thickness, handle to become easily, by being below the 50 μ m, bending is easily installed and is become easy.
Need to prove that the resin combination of present embodiment can also use as photosensitive polymer combination owing to contain (D) sensitizer.In addition, by photosensitive polymer combination is coated on the base material, can also obtain photosensitive film.
In addition, consider that from the aspect that improves flame retardant resistance the resin combination of present embodiment can also contain (F) phosphorus compound and use.As (F) phosphorus compound, can use phosphate compound or phosphazene compound etc.
In addition, the resin combination of present embodiment is by arranging resin combination and dry at Copper Foil, can suit as the interlayer dielectric of layer flexible wiring board etc.In addition, the resin combination of present embodiment arranges resin combination by the wiring trace that is formed on the base material with covering, can suit as the protective membrane of the Wiring pattern of wiring board.
Need to prove that except polyimide, 2 officials energy hydroxy-containing compounds, oxazoline compound, resin combination can also contain organic solvent.This is because by for being dissolved in the state of organic solvent, can preferably use as varnish.
As such organic solvent, can enumerate N, the N-N,N-DIMETHYLACETAMIDE, N, the N-diethyl acetamide, N, dinethylformamide, N, the N-diethylformamide, amide solvents such as N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, ester solvent in the γ-Wu Neizhi etc., dimethyl sulfoxide (DMSO), diethyl sulfoxide, sulfur-bearing series solvents such as hexamethyl sulfoxide, cresols, phenol series solvents such as phenol, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethyleneglycol dimethyl ether, dioxane, tetrahydrofuran (THF), butyl benzoate, ethyl benzoate, ether solvents such as methyl benzoate.In addition, these organic solvents can use separately, also can share two or more.Particularly, consider from the aspect of high boiling point and low water absorbable, preferably use gamma-butyrolactone, triglyme, butyl benzoate, ethyl benzoate.
Embodiment
Below, the embodiment that carries out for clear and definite effect of the present invention is described.Need to prove that the present invention is not subjected to any restriction of following embodiment.
About the resin combination of the 1st embodiment of the present invention, describe with reference to following embodiment 1 and comparative example 1.Need to prove that in following embodiment 1, sample 1 is the resin combination of the 2nd mode to sample 32, sample 33 to sample 35 is the resin combination of the 1st mode.
(embodiment 1)
Making comprises the sample 1 of the cured film of resin combination, has confirmed its characteristic.In the present embodiment, as resin combination, using in the imidization rate is that the chemistry society of Asahi Chemical Industry that has added as polycarbonate diol in the varnish of 88% polyimide (hereinafter referred to as polyimide A) makes DURANOL T5651 (molecular weight 1000; Hereinafter referred to as multifunctional hydroxy-containing compounds A) and be that the Asahi Chemical Industry chemistry society of blocked isocyanate makes DURANATE SBN-70D (NCO content 10.2wt% as hexamethylene diisocyanate; Hereinafter referred to as isocyanate compound A) material.With respect to polyimide A100 mass parts, multifunctional hydroxy-containing compounds A is 5 mass parts, and isocyanate compound A is 5 mass parts.In addition, with respect to resin combination, be that the mode of 30 quality % is concocted with polyimide A.In this case, the mol ratio of the isocyanate group that contains of the hydroxyl that contains of multifunctional hydroxy-containing compounds and isocyanate compound A is hydroxyl/isocyanate base=0.9.Below, the synthetic method of polyimide A, the making method of cured film and the evaluation method of each characteristic are described.
[polyimide A]
Synthetic method to polyimide A describes.At first, at three mouthfuls of removable flasks nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture seperating vale.Add JEFFAMINE XTJ-542 (manufacturing of Huntsman society, weight-average molecular weight 1000) 40g, 10 ℃ of ice-water bath, 3-two (3-amino-benzene oxygen) benzene (APB) 23.519g, Tetra hydro Phthalic anhydride 2.027g, gamma-butyrolactone (GBL) 60g, ethyl benzoate (BAEE) 60g, toluene 20g, γ-Wu Neizhi 12g, pyridine 18g are stirred to evenly.In addition, add 3,3 ', 4 bit by bit, 4 '-benzophenone tetracarboxylic dianhydride (BTDA) 18.966g and 3,3 ', 4,4 '-diphenylsulfone acid dianhydride (DSDA) 19.616g.Stir after 0.5 hour, be warming up to 170 ℃, heated 4 hours.In the reaction, water and methylbenzene azeotropic that by-product is given birth to use the spherical condensation tube that possesses the moisture seperating vale to dewater under refluxing.After removing the living water of by-product, stop to reflux, toluene is all removed.After system is cooled to 60 ℃, add BTDA5.293g, APB4.780g.After 5 hours, be cooled to room temperature.Then with the strainer of 5 μ m with resultant pressure filtration, be 88% polyimide A varnish thereby obtain the imidization rate.
Need to prove that above-mentioned imidization rate utilizes the IR method to try to achieve.Specifically, with based on 1480cm -1Near the peak of phenyl ring as benchmark, by with based on 1380cm -1The ratio of the absorbancy at the peak that near imide ring generates is obtained the imidization rate.About the imidization rate C under the arbitrary temp, with the 1480cm under the arbitrary temp -1Absorbancy be made as A3, with 1380cm -1Absorbancy be made as B3, calculated by the formula of C=((B3/A3-B1/A1)/(B2/A2-B1/A1)) * 100 (%).Herein, will 50 ℃ synthetic, 80 ℃ of dried resin at 1480cm -1The absorbancy at place is made as A1, with 1380cm -1Absorbancy be made as B1.In addition, will be in air atmosphere the resin of 220 ℃ of thermal treatments after 60 minutes at 1480cm -1The absorbancy at place is made as A2, with 1380cm -1Absorbancy be made as B2.In addition, about each peak, with the suitable draw base line of mode of the Gu Yugu that links the peak, will be defined as absorbancy separately from the height at each peak of baseline (that is the distance between the intersection point of the line of each peak dot and the decline from each peak to baseline and baseline) before and after the peak.Need to prove that the imidization rate C that calculates in the above-mentioned formula is that the imidization rate during with thermal treatment in 220 ℃, 60 minutes is made as 100% value.
[making of cured film]
Above-mentioned resin combination is coated with machine with rod coats substrate, at room temperature carry out leveling in 5 minutes～10 minutes,, next heated 30 minutes and dry solidification at 180 ℃ 120 ℃ of heating 60 minutes with hot-air oven, make sample 1.As substrate, KAPTON (registered trademark) 100EN that uses society of Dong Li Du Pont to make.In addition, resin combination is coated the single face of substrate.Thickness behind the dry solidification is about 20 μ m.
[evaluation of warpage]
About the evaluation of warpage, estimate according to the rise of four jiaos on sample.Specifically, under 23 ℃, the environment of humidity 50%, said sample 1 is cut into 5cm * 5cm, will measure as warpage with respect to the distance of floating at the angle of central part.It is good that warpage is that 10mm is evaluated as when following, is designated as zero, for 5mm is evaluated as when following better, is designated as ◎, for 15mm is designated as △ when following, is evaluated as badly when surpassing 15mm, be designated as *.
[evaluation of scolder patience (thermotolerance)]
About scolder patience, according to the JPCA-BM02 standard, the sample 1 that will cut into 3cm * 3cm is at 260 ℃ of dippings 60 seconds and estimating in solder bath.By visual inspection Check outward appearance, confirm to have or not variations such as distortion and dissolving vestige, the situation about find changing more than 90% of the total area is designated as zero, 50%～90% of the total area is found that situation about changing is designated as △, with the zone not finding to change less than 50% situation be designated as *.
[evaluation of chemical proofing]
Said sample 1 was at room temperature flooded 10 minutes in methyl ethyl ketone, by the visual inspection appearance of film, confirm to have or not variations such as distortion and dissolving vestige.The situation about find changing more than 90% of the total area is designated as zero, 50%～90% of the total area is found that situation about changing is designated as △, with the zone not finding to change less than 50% situation be designated as *.
[evaluation of the insulation resistance under 85 ℃ of humidity 85% conditions of temperature]
As the base material of the tellite of flexibility, use ESPANEX M (chemistry society of Nippon Steel makes) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)), make live width/line-spacing: the comb shape wiring board of 50 μ m/50 μ m.With the thickness after solidifying be the mode of 15 μ m on this circuit substrate a part of coating resin composition and make its curing, as sample 1B.The condition of solidifying is identical with sample 1A.Yi Bian under DC50V, 85 ℃, the condition of humidity 85% place 8 hour, Yi Bian measure resistance, insulation resistance surpassed 10 thereafter, 9The situation of Ω is designated as zero, will not reach 10 9The situation of Ω is designated as *.
[evaluation of 100 ℃ to 220 ℃ viscosity]
Viscosity about 100 ℃ to 220 ℃, use TA INSTRUMENTS society to make mensuration machine AR-G2, from removing Copper Foil and obtain resin molding as the resin molding etching of base material with Copper Foil, 27 above-mentioned resin moldings of lamination, use resulting sample, with rotor: diameter 8mm parallel plate, distortion: the condition of frequency 0.1%: 1Hz, method uniaxial stress: 0.1N (100g) is estimated.Be that the situation of the scope of 5000Pas to 100000Pas is designated as zero with 100 ℃ to 220 ℃ viscosity, will be designated as less than 5000Pas or the situation that surpasses the zone of 100000Pas *.
[evaluation of elastic part and plasticity part]
About elastic part and plasticity part, according to the JIS-C-2151 standard, apart from the condition of 50mm, 100mm/min the sample of wide 5mm, long 100mm is carried out tension test between chuck, elongation till yield-point is evaluated as elastic part, the elongation of yield-point till the breaking point is evaluated as the plasticity part.With elastic part less than 20%, elongation is that the situation of the plasticity part more than 50% is designated as zero, be 20% or more with elastic part or elongation less than 50% plasticity situation partly be designated as *.
[evaluation of layer insulation resistance]
About layer insulation resistance, use ESPANEX M (chemistry society of Nippon Steel makes) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)) as the base material of flexible tellite, to carrying out lamination with Copper Foil as the resin molding of base material, thereafter, measuring resistance in 1000 hours while placing under DC50V, 85 ℃, the condition of humidity 85%, is 10 with the insulation resistance between the resin molding 9The above situation of Ω is designated as zero, will not reach 10 9The situation of Ω is designated as *.
[evaluation of through hole imbedibility]
About the through hole imbedibility, with Resins, epoxy 4 layers wiring board of made is carried out embedding, cut off also and grind, utilize the opticmicroscope evaluation.There is the situation of resin to be designated as zero with seamlessly embedding in the through hole, the situation of observing the gap in the through hole is designated as *.
[evaluation of cold shock testing]
About cold shock testing, according to the JPCA-HD01-2003 standard, with-40 ℃, 120 ℃, 1000 the circulation 4 layers wiring board of made is estimated.Be 10% to be designated as zero with interior situation with the change of connection resistance in the circulation, will be designated as above 10% situation *.
[evaluation of Resin Flow]
About Resin Flow, will with Copper Foil as the square resin sheet and Copper Foil F2-WS (12 μ m) vacuum pressing (180 ℃, 20 minutes, 4MPa) lamination of the 20cm of base material after, the overflowing of the resin by visual valuation sample end.With overflowing for the situation below the 1mm is designated as zero of resin, will be designated as above the situation of 1mm *.
The evaluation result of sample 1 (sample 1A, sample 1B) is listed in the table below 1.By following table 1 as can be known, the warpage when having used the cured article of the resin combination of sample 1 fully to suppress to solidify, scolder patience (being thermotolerance) excellence.In addition, the insulativity of chemical proofing and hot and humid condition is also excellent as can be known.
In addition, the cured article of resin combination that has used sample 1 in the evaluation of elastic part and plasticity part, layer insulation resistance, through hole imbedibility, cold shock testing, Resin Flow any one in all obtained good evaluation result.
Then, use the resin combination of under the condition different with sample 1, concocting to make cured film, confirmed the characteristic of the sample 2～sample 21 of made.
[sample 2～sample 5]
About sample 2～sample 5, with sample 1 similarly, use the resin combination comprise polyimide A, multifunctional hydroxy-containing compounds A, isocyanate compound A to make.The main difference point of sample 2～sample 5 is the content of multifunctional hydroxy-containing compounds A and isocyanate compound A.Specifically, sample 2 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds A7.5 mass parts, isocyanate compound A7.5 mass parts.Sample 3 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds A10 mass parts, isocyanate compound A10 mass parts.Sample 4 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds A15 mass parts, isocyanate compound A15 mass parts.Sample 5 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds A10 mass parts, isocyanate compound A15 mass parts.The making method of sample 2～sample 5 and evaluation method etc. are identical with sample 1.
[sample 6～sample 9]
About sample 6～sample 9, it is that 28% polyimide (hereinafter referred to as polyimide B), the resin combination of multifunctional hydroxy-containing compounds A, isocyanate compound A are made that use comprises imidization rate described later.The main difference point of sample 6～sample 9 is the content of multifunctional hydroxy-containing compounds A and blocked isocyanate A.Specifically, sample 6 uses are made with respect to the resin combination that polyimide B100 mass parts has added multifunctional hydroxy-containing compounds A7.5 mass parts, isocyanate compound A7.5 mass parts.Sample 7 uses are made with respect to the resin combination that polyimide B100 mass parts has added multifunctional hydroxy-containing compounds A10 mass parts, isocyanate compound A10 mass parts.Sample 8 uses are made with respect to the resin combination that polyimide B100 mass parts has added multifunctional hydroxy-containing compounds A30 mass parts, isocyanate compound A30 mass parts.Sample 9 uses are made with respect to the resin combination that polyimide B100 mass parts has added multifunctional hydroxy-containing compounds A60 mass parts, isocyanate compound A60 mass parts.About the making method of sample 6～sample 9 and evaluation method etc., identical with sample 1.
[polyimide B]
The synthetic method of polyimide B is as follows.At first, at three mouthfuls of removable flasks nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture seperating vale.Add JEFFAMINE XTJ-542 (manufacturing of Huntsman society, weight-average molecular weight 1000) 40g, gamma-butyrolactone (GBL) 60g, ethyl benzoate (BAEE) 60g, toluene 20g, γ-Wu Neizhi 12g, pyridine 18g 0 ℃ of ice-water bath, be stirred to evenly.In addition, add 3,3 ', 4 bit by bit, 4 '-biphenyl tetracarboxylic dianhydride (BPDA) 11.760g.Stir after 0.5 hour, be warming up to 170 ℃, heated 4 hours.In the reaction, water and methylbenzene azeotropic that by-product is given birth to use the spherical condensation tube that possesses the moisture seperating vale to dewater under refluxing.After removing the living water of by-product, stop to reflux, toluene is all removed.After system is cooled to 60 ℃, add BPDA35.6g, APB29.738g.After 5 hours, be cooled to room temperature.Then with the strainer of 5 μ m with resultant pressure filtration, be 28% polyimide B varnish thereby obtain the imidization rate.
[sample 10～sample 15]
Sample 10～sample 15 uses the resin combination that comprises polyimide A, isocyanate compound A to make.The main difference point of sample 10～sample 15 is to have used among multifunctional hydroxy-containing compounds B～F any one as multifunctional hydroxy-containing compounds.As multifunctional hydroxy-containing compounds B, used the chemistry society of Asahi Chemical Industry as polycarbonate diol to make DURANOL T5652 (molecular weight 2000).As multifunctional hydroxy-containing compounds C, used the chemistry society of Asahi Chemical Industry as polycarbonate diol to make DURANOL T4671 (molecular weight 1000).As multifunctional hydroxy-containing compounds D, used the Japanese Cao Da manufacturing G-1000 (molecular weight 1000) of society as polybutadiene diol.As multifunctional hydroxy-containing compounds E, used the Japanese Cao Da manufacturing GI-1000 (molecular weight 1000) of society as the hydrogenated butadiene polymer glycol.As multifunctional hydroxy-containing compounds F, used the Mitsubishi Chemical society as polytetramethylene glycol to make PTMG1000 (molecular weight 1000).
Sample 10 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds B10 mass parts, isocyanate compound A5 mass parts.Sample 11 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds C10 mass parts, isocyanate compound A10 mass parts.Sample 12 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds D30 mass parts, isocyanate compound A30 mass parts.Sample 13 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds E30 mass parts, isocyanate compound A30 mass parts.Sample 14 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds F30 mass parts, isocyanate compound A30 mass parts.Sample 15 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds B7.5 mass parts, isocyanate compound A7.5 mass parts.About the making method of sample 10～sample 15 and evaluation method etc., identical with sample 1.
[sample 16, sample 17]
Sample 16, sample 17 use the resin combination that comprises polyimide A, multifunctional hydroxy-containing compounds A to make.The main difference point of sample 16, sample 17 is to have used among isocyanate compound B, the C any one as isocyanate compound.As isocyanate compound B, having used as hexamethylene diisocyanate is that the Asahi Chemical Industry chemistry society of blocked isocyanate makes DURANATE TPA-B80E (NCO content=12.5wt%).As isocyanate compound C, having used as isophorone diisocyanate is the model 7951 made of the Baxenden society of blocked isocyanate (NCO content=7.80wt%).
Sample 16 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds A10 mass parts, isocyanate compound B9 mass parts.Sample 17 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds A10 mass parts, isocyanate compound C14 mass parts.About the making method of sample 16, sample 17 and evaluation method etc., identical with sample 1.
[sample 18, sample 19]
Sample 18, sample 19 use the resin combination that comprises polyimide B, multifunctional hydroxy-containing compounds A, isocyanate compound A to make.The main difference point of sample 18, sample 19 is the content of multifunctional hydroxy-containing compounds A and isocyanate compound A and the heating condition when solidifying.Specifically, sample 18 uses are made with respect to the resin combination that polyimide B100 mass parts has added multifunctional hydroxy-containing compounds A10 mass parts, isocyanate compound A10 mass parts.Sample 19 uses are made with respect to the resin combination that polyimide B100 mass parts has added multifunctional hydroxy-containing compounds A30 mass parts, isocyanate compound A30 mass parts.In addition, the heating condition during curing is 180 ℃, 60 minutes, then 180 ℃, 60 minutes (that is, 180 ℃, 60 minutes * 2).About the making method of the sample 18 except heating condition, sample 19, evaluation method etc., identical with sample 1.
[sample 20, sample 21]
Sample 20, sample 21 similarly use the resin combination that comprises polyimide A, multifunctional hydroxy-containing compounds A, isocyanate compound A to make with sample 1.The main difference point of sample 20, sample 21 is the content of multifunctional hydroxy-containing compounds A and isocyanate compound A.Specifically, sample 20 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds A3 mass parts, isocyanate compound A3 mass parts.Sample 21 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds A70 mass parts, isocyanate compound A70 mass parts.The making method of sample 20, sample 21 and evaluation method etc. are identical with sample 1.
The evaluation result of sample 2～sample 21 is listed in the table below 1.By following table 1 as can be known, the warpage when having used the cured article of the resin combination in the present embodiment fully to suppress to solidify, scolder patience (being thermotolerance) excellence.In addition, the insulativity of chemical proofing and hot and humid condition is also excellent.Need to prove, by the evaluation result of sample 10～sample 15 grades as can be known, consider from the aspect that improves insulativity, as multifunctional hydroxy-containing compounds, preferably use polybutadiene diol, hydrogenated butadiene polymer glycol, polycarbonate diol.In addition we know, consider from the aspect that reduces warpage, with respect to resin combination 100 mass parts, preferably contain 3 mass parts～70 mass parts polyimide at least, more preferably contain 5 mass parts～70 mass parts, further preferably contain 5 mass parts～60 mass parts.In addition, by the evaluation result of sample 18, sample 19 etc. as can be known, consider from the aspect that improves thermotolerance and chemical proofing, preferably use the thermal treatment of low-temperature region (100～130 ℃) and the thermal treatment of high-temperature area (160～200 ℃) in the lump.Wherein, heat treated condition is not limited to this.
Then, use the resin combination of under the condition different with sample 1～sample 21, concocting to make cured film, confirmed the characteristic of the sample 22～sample 29 of made.
[sample 22～sample 25]
Sample 22～sample 25 uses the resin combination and the sample 1 that comprise polyimide C～F, multifunctional hydroxy-containing compounds A, isocyanate compound A similarly to make.The main difference point of sample 22～sample 25 is the imidization rate of polyimide.Specifically, 25 uses of sample 22～sample are made with respect to the resin combination that polyimide C～F100 mass parts has added multifunctional hydroxy-containing compounds A15 mass parts, isocyanate compound A15 mass parts.The making method of sample 22～sample 25 and evaluation method etc. are identical with sample 1.
[polyimide C]
Synthetic method to polyimide C describes.At first, at three mouthfuls of removable flasks nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture seperating vale.Add triethylene glycol dimethyl ether 15g, gamma-butyrolactone 35g, toluene 20.0g, 4 under 25 ℃ of room temperatures, the two O-phthalic acid dianhydrides of 4 '-oxygen (Manac society makes, is called for short ODPA) 10.86g (35.00mmol) is stirred to evenly., be warming up to 80 ℃, add silicone diamine (chemical industry society of SHIN-ETSU HANTOTAI makes, is called for short KF-8010) 11.30g (13.78mmol), and then after stirring 0.5 hour, be warming up to 170 ℃, heated 4 hours thereafter.In the reaction, water and methylbenzene azeotropic that by-product is given birth to use the spherical condensation tube that possesses the moisture seperating vale to dewater under refluxing.After removing the living water of by-product, stop to reflux, toluene is all removed.After system is cooled to 100 ℃, adds maleic anhydride 0.14g and also stirred 0.5 hour.After leaving standstill 12 hours, cooling under 25 ℃ of room temperatures, add two (3-amino-benzene oxygen) benzene of 1,3-(Mitsui Chemicals society makes, is called for short APB-N) 6.00g (20.52mmol).Under 25 ℃ of room temperatures, stirred 5 hours.Then with the strainer of 5 μ m with resultant pressure filtration, be 40% polyimide C varnish thereby obtain the imidization rate.
[polyimide D]
Synthetic method to polyimide D describes.At first, at three mouthfuls of removable flasks nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture seperating vale.Under 25 ℃ of room temperatures, add triethylene glycol dimethyl ether 15g, gamma-butyrolactone 35g, toluene 20.0g, ODPA10.86g (35.00mmol), be stirred to evenly., be warming up to 80 ℃, add KF-801011.30g (13.78mmol), and then after stirring 2 hours, add primary APB-N2.17g (7.42mmol) and stirred 0.5 hour, be warming up to 170 ℃ then, heated 4 hours thereafter.In the reaction, water and methylbenzene azeotropic that by-product is given birth to use the spherical condensation tube that possesses the moisture seperating vale to dewater under refluxing.After removing the living water of by-product, stop to reflux, toluene is all removed.After system is cooled to 100 ℃, adds maleic anhydride 0.14g and also stirred 0.5 hour.Leave standstill under 25 ℃ of room temperatures 12 hours, the cooling after, add secondary APB-N3.83g (13.10mmol).Under 25 ℃ of room temperatures, stirred 5 hours.Then with the strainer of 5 μ m with resultant pressure filtration, be 60% polyimide D varnish thereby obtain the imidization rate.
[polyimide E]
Synthetic method to polyimide E describes.Except the primary APB-N of the synthetic method that makes polyimide F is 4.03g (13.78mmol), to make secondary APB-N be the 1.97g (6.73mmol), similarly obtaining the imidization rate with the synthetic method of polyimide D is 80% polyimide E varnish.
[polyimide F]
Synthetic method to polyimide F describes.Except the primary APB-N of the synthetic method that makes polyimide D is 4.86g (16.62mmol), to make secondary APB-N be the 1.03g (3.52mmol), similarly obtaining the imidization rate with the synthetic method of polyimide D is 90% polyimide F varnish.
[sample 26]
Sample 26 uses the resin combination and the sample 1 that comprise polyimide C, multifunctional hydroxy-containing compounds A, isocyanate compound A similarly to make.With respect to sample 22, the main difference of sample 26 point is the interpolation of flame-retardant composition.Specifically, sample 26 uses and has added multifunctional hydroxy-containing compounds A15 mass parts, isocyanate compound A15 mass parts, volt with respect to polyimide C100 mass parts and see that the resin combination of phosphine carbonitrile derivatives FP-300 (fire retardant A) 23 mass parts that society of pharmacy institute makes makes.The making method of sample 26 and evaluation method etc. are identical with sample 1.
[sample 27]
Sample 27 uses the resin combination identical with sample 26 to make.With respect to sample 26, the main difference of sample 27 point is the substrate for [making of cured film].Specifically, in the sample 27, use the 12 μ m thickness product of the Copper Foil F2-WS that Furukawa Circuit Foil society makes as substrate, form cured film at the uneven surface of Copper Foil.Thickness behind the dry solidification is about 30 μ m.Other making methods of sample 27 and evaluation method etc. are identical with sample 1.
[sample 28]
Sample 28 uses the resin combination and the sample 1 that comprise polyimide C, multifunctional hydroxy-containing compounds A, isocyanate compound A similarly to make.With respect to sample 22, the main difference of sample 28 point is the interpolation of flame-retardant composition and the interpolation of catalyzer.Sample 28 uses and has added multifunctional hydroxy-containing compounds A18 mass parts with respect to polyimide C100 mass parts, isocyanate compound A18 mass parts, volt is seen phosphine carbonitrile derivatives FP-300 (fire retardant A) 27 mass parts that society of pharmacy institute makes, the melamine cyanurate MC-20NJ that Sakai chemical industry society makes pulverizes product (fire retardant B: median size 1.1 μ m, maximum particle diameter 3 μ m) 18 mass parts, the resin combination of U-CAT SA (registered trademark) 102 (catalyst A) 0.18 mass parts that San-Apro society makes is made.About the making method of sample 28 and evaluation method etc., the 12 μ m thickness product of the Copper Foil F2-WS that use Furukawa Circuit Foil society makes are as substrate, uneven surface at Copper Foil forms cured film, heated 15 minutes and dry solidification 120 ℃ of heating 10 minutes and at 200 ℃, make the thickness after the curing be about 30 μ m, identical with sample 1 in addition.
[sample 29]
Sample 29 uses the resin combination identical with sample 28 to make.With respect to sample 28, the main difference point of sample 29 only is catalyst type.Specifically, U-CAT (registered trademark) 1102 (catalyst B) 0.18 mass parts of using San-Apro society to make.Other making methods of sample 29 and evaluation method etc. are identical with sample 28.
The evaluation result of sample 22～sample 29 is listed in the table below 2.By following table 2 as can be known, the warpage when having used the cured article of the resin combination of sample 22～sample 29 fully to suppress to solidify, scolder patience (being thermotolerance) excellence.In addition, the insulativity of chemical proofing and hot and humid condition is also excellent, has obtained with the sample 1 shown in the following table 1 to the same effect of the resin combination of sample 21.
Then, use the resin molding of making in sample 27～sample 29 to make sample 30～sample 32, confirmed its characteristic.
[sample 30]
Sample 30 uses the resin molding that obtains in the sample 27 to make.With respect to sample 27, the main difference of sample 30 point is that the lamination resin molding is made on wiring board.Specifically, base material as the printed circuit board (PCB) of flexibility, use ESPANEX M (chemistry society of Nippon Steel makes) (thickness of insulation layer is that 25 μ m, conductor layer are Copper Foil F2-WS (18 μ m)), at interval the through hole of diameter 0.1mm is holed after processing and the copper facing with 4mm, two sides vacuum pressing (180 ℃, 20 minutes, 4MPa) laminated resin film at the wiring board of processing through pattern, pattern processing back central authorities between through hole carry out laser via processing and copper facing, make 4 layers the wiring board that 25 through hole daisy chains are connected.
[sample 31, sample 32]
Sample 31 uses samples 28, sample 32 to use samples 29, utilizes the method identical with sample 30 to make wiring board, the method evaluation that utilization and sample 30 are identical.
Then, use the resin combination of under the condition different with sample 1～sample 32, concocting to make resin molding, confirmed the characteristic of the sample 33～sample 35 of made.
[sample 33]
Sample 33 uses and has added multifunctional hydroxy-containing compounds A and be that the chemistry society of Asahi Chemical Industry of isocyanic ester makes DURANATE TPA-100 (NCO content is 23.1wt% as hexamethylene diisocyanate in the imidization rate is the varnish of 100% polyimide G; Hereinafter referred to as isocyanate compound C) material.With respect to polyimide G100 mass parts, multifunctional hydroxy-containing compounds A is 10 mass parts, and isocyanate compound C is 4.4 mass parts.In addition, with respect to resin combination, be that the mode of 30 quality % is concocted with polyimide G.In this case, the mol ratio of the isocyanate group that contains of the hydroxyl that contains of multifunctional hydroxy-containing compounds and isocyanate compound D is hydroxyl/isocyanate base=0.9.Use this resin combination, utilize the method identical with sample 30 to make wiring board, the method evaluation that utilization and sample 30 are identical.
[polyimide G]
Synthetic method to polyimide G describes.At first, at three mouthfuls of removable flasks nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture seperating vale.Add triethylene glycol dimethyl ether 15g, gamma-butyrolactone 35g, toluene 20.0g, 4 under 25 ℃ of room temperatures, the two O-phthalic acid dianhydrides of 4 '-oxygen (Manac society makes, is called for short ODPA) 10.86g (35.00mmol) is stirred to evenly., be warming up to 80 ℃, add silicone diamine (chemical industry society of SHIN-ETSU HANTOTAI makes, is called for short KF-8010) 11.30g (13.78mmol), and then after stirring 0.5 hour, be warming up to 170 ℃, heated 4 hours thereafter.In the reaction, water and methylbenzene azeotropic that by-product is given birth to use the spherical condensation tube that possesses the moisture seperating vale to dewater under refluxing.After removing the living water of by-product, stop to reflux, toluene is all removed.After system is cooled to 100 ℃, adds maleic anhydride 0.14g and also stirred 0.5 hour.After leaving standstill 12 hours, cooling under 25 ℃ of room temperatures, add two (3-amino-benzene oxygen) benzene of 1,3-(Mitsui Chemicals society makes, is called for short APB-N) 6.00g (20.52mmol), gamma-butyrolactone 35g, toluene 20.0g.Stir after 0.5 hour, be warming up to 170 ℃, heated 4 hours.In the reaction, water and methylbenzene azeotropic that by-product is given birth to use the spherical condensation tube that possesses the moisture seperating vale to dewater under refluxing.After removing the living water of by-product, stop to reflux, toluene is all removed.Then with the strainer of 5 μ m with resultant pressure filtration, be 100% polyimide G varnish thereby obtain the imidization rate.
[sample 34]
Sample 34 uses and added the material of making DURANOL T5650E (molecular weight 500) and isocyanate compound D as the chemistry society of Asahi Chemical Industry of polycarbonate diol in the varnish of polyimide G.With respect to polyimide G100 mass parts, T5650E is 5 mass parts, and isocyanate compound D is 4.4 mass parts.In addition, with respect to resin combination, be that the mode of 30 quality % is concocted with polyimide H.In this case, the mol ratio of the isocyanate group that contains of the hydroxyl that contains of multifunctional hydroxy-containing compounds and isocyanate compound D is hydroxyl/isocyanate base=0.9.Use this resin combination to utilize the method identical with sample 30 to make wiring board, the method evaluation that utilization and sample 30 are identical.
[sample 35]
Sample 35 uses the average hydroxyl number that has added as polycarbonate polyol in the varnish of polyimide G be 3.6 polycarbonate polyol A and the material of hexamethylene diisocyanate (hereinafter referred to as isocyanate compound E).With respect to polyimide G100 mass parts, polycarbonate polyol A is 6.2 mass parts, and hexamethylene diisocyanate is 2 mass parts.In addition, with respect to resin combination, be that the mode of 30 quality % is concocted with polyimide G.In this case, the mol ratio of the isocyanate group that contains of the hydroxyl that contains of multifunctional hydroxy-containing compounds and isocyanate compound E is hydroxyl/isocyanate base=0.9.Use this resin combination to utilize the method identical with sample 30 to make wiring board, the method evaluation that utilization and sample 30 are identical.The evaluation result of sample 30～sample 35 is listed in the table below 3.
[polycarbonate polyol A]
Synthetic method to polycarbonate polyol A describes.In 2 liters of flasks that have distillation tower (having filled diameter 10mm, the length 300mm of Dixon filler) and thermometer, stirrer, add ethylene carbonate: EC871.6g (9.9 moles), TriMethylolPropane(TMP): TMP530.8g (3.96 moles), 1.6-hexylene glycol: HDL351.6g (2.98 moles), 1,5-pentanediol: PDL310g (2.98 moles), heated and stirred under the decompression of 20torr, temperature is 120 ℃～130 ℃ in the control.Top from distillation tower distillates EC and the ethylene glycol that azeotropic is formed on one side, Yi Bian carry out reaction in 18 hours.Then dismantle distillation tower, making vacuum tightness is 4Torr, reclaims unreacted EC and glycol.Unreacted reactant distillate termination after, temperature is 190 ℃ in making, and keeping under the state of this temperature glycol being distillated, carries out self-condensation reaction thus.After reacting 5 hours, utilize GPC (gel permeation chromatography) to analyze and obtain the liquid that number-average molecular weight is the water white viscosity of 1014 (polystyrene conversion).Productive rate is 1200g.This liquid has following rerum natura.Forming (mole %) is HDL:PDL:TMP=30.0:21.7:45.4, and other unit that comprise ehter bond exist 0.4%, OH value (mgKOH/g)=198.8, average hydroxyl number=3.6.
[evaluation of the molecular weight of multifunctional hydroxy-containing compounds]
The molecular weight of multifunctional hydroxy-containing compounds utilizes gel permeation chromatography (Dong Caoshe manufacturing) to measure, and utilizes the number-average molecular weight evaluation of vinylbenzene conversion molecular weight.
By following table 3 as can be known, used layer insulation resistance, through hole imbedibility, scolder patience (be thermotolerance), the thermal shock patience excellence of sample 30 to the resin molding of the resin combination of sample 35, obtained with the sample 1 shown in the following table 1 to the same effect of the resin combination of sample 21.In addition we know, to use the imidization rate be (sample 33～sample 35) under the situation of 100% polyimide, use (sample 35) under the situation of the multifunctional hydroxy-containing compounds that 3 officials can be above, use 2 officials can the situation of isocyanate compound under (sample 35), use under the situation of blocked isocyanate isocyanate compound in addition (sample 33～sample 35), also obtained good result.
(comparative example 1)
As a comparative example, use the resin combination of under the condition different with above-described embodiment 1, concocting to make cured film, confirmed the characteristic of the sample of made.In this comparative example, make duplicate 1～duplicate 8, confirmed its characteristic.
[duplicate 1～duplicate 3]
Duplicate 1～duplicate 3 uses the resin combination that comprises polyimide A to make.The main difference point of duplicate 1～duplicate 3 is the composition beyond the polyimide A.Specifically, duplicate 1 uses the resin combination that does not comprise multifunctional hydroxy-containing compounds A and isocyanate compound A to make.Duplicate 2 uses are made with respect to the resin combination that polyimide A100 mass parts has added multifunctional hydroxy-containing compounds A5 mass parts.Duplicate 3 uses are made with respect to the resin combination that polyimide A100 mass parts has added isocyanate compound A5 mass parts.The making method of duplicate 1～duplicate 3 and evaluation method etc. are identical with embodiment 1.
[duplicate 4, duplicate 5]
Duplicate 4, duplicate 5 use the resin combination that comprises polyimide A, multifunctional hydroxy-containing compounds A, isocyanate compound A to make.Duplicate 4,5 main difference point are that isocyanate compound A is with respect to the content of multifunctional hydroxy-containing compounds A (that is the mol ratio of the isocyanate group that contains of the hydroxyl that contains of multifunctional hydroxy-containing compounds and isocyanate compound A).More particularly, thus duplicate 4 use with respect to polyimide A100 mass parts added multifunctional hydroxy-containing compounds A10 mass parts, isocyanate compound A6 mass parts makes the mol ratio of hydroxyl and isocyanate group make as the resin combination of hydroxyl/isocyanate base=1.4.Duplicate 5 use with respect to polyimide A100 mass parts added multifunctional hydroxy-containing compounds A10 mass parts, thereby isocyanate compound A20 mass parts makes the mol ratio of hydroxyl and isocyanate group make as the resin combination of hydroxyl/isocyanate base=0.4.Duplicate 4,5 making method and evaluation method etc. are identical with embodiment 1.
[duplicate 6]
Duplicate 6 uses the resin combination that comprises multifunctional hydroxy-containing compounds A, isocyanate compound A to make.That is, duplicate 6 uses the resin combination that does not comprise polyimide to make.The making method of duplicate 6 and evaluation method etc. are identical with embodiment 1.
[duplicate 7]
Duplicate 7 uses that to comprise multifunctional hydroxy-containing compounds and blocked isocyanate the imidization rate in the skeleton of entering be 100% the polyimide (polyimide that does not comprise the polyamic acid structure; Hereinafter referred to as polyimide H) resin combination make.Because multifunctional hydroxy-containing compounds and blocked isocyanate enter among the polyimide H, therefore as the composition of resin combination, do not comprise multifunctional hydroxy-containing compounds and blocked isocyanate.The making method of duplicate 7 and evaluation method etc. are identical with embodiment 1.
[polyimide H]
The synthetic method of polyimide H is as follows.At first, in three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture seperating vale.Drop into chemistry society of Asahi Chemical Industry and make DURANOL T5651 (molecular weight 1000) 78.88g, hexamethylene diisocyanate 26.91g, gamma-butyrolactone (GBL) 177g.After stirring 15 minutes with 200rpm under room temperature, the nitrogen atmosphere, be warming up to 140 ℃ and stirred 1 hour.Then, add 4,4 '-oxygen two O-phthalic acid dianhydride 62.04g (200 mmole), GBL176g with 170 ℃, 200rpm stirring, reacted 1.5 hours on one side on one side.In addition, be cooled to room temperature, add BPDA5.88g, APB40.55g, GBL353g, toluene 70g, γ-Wu Neizhi 2.2g, pyridine 3.5g, on one side with 170 ℃, 200rpm stirring, reacted 3.5 hours on one side.In the reaction, water and methylbenzene azeotropic that by-product is given birth to use the spherical condensation tube that possesses the moisture seperating vale to dewater under refluxing.After removing the living water of by-product, stop to reflux, toluene is all removed.Then with the strainer of 5 μ m with resultant pressure filtration, be 100% polyimide H varnish thereby obtain the imidization rate.That is, polyimide H is equivalent to not comprise in the polyimide in resin combination the polyamic acid structure and does not enter material in the skeleton of polyimide as the composition in the resin combination with multifunctional hydroxy-containing compounds and blocked isocyanate.
The evaluation result of duplicate 1～duplicate 7 is listed in the table below 4.Can be confirmed by duplicate 1～3,6: under any one the situation in lacking polyimide, multifunctional hydroxy-containing compounds, isocyanate compound, can't obtain good cured article.In addition, can be confirmed by duplicate 4,5: under the situation of excessive hydroxyl/isocyanate base=0.4 of isocyanate compound, produce warpage by isocyanate compound reaction each other, under the situation of excessive hydroxyl/isocyanate base=1.4 of multifunctional hydroxy-containing compounds, unreacted reactant increases, and chemical proofing reduces.That is, confirm under the situation that is not hydroxyl/isocyanate base=0.5～1, can't obtain good cured article.In addition, can be confirmed by duplicate 7: enter in the skeleton at multifunctional hydroxy-containing compounds and isocyanate compound, do not comprise under the situation of multifunctional hydroxy-containing compounds and isocyanate compound as the composition of resin combination, can't obtain good cured article.
[table 1]
Figure BDA00003375991600761
[table 2]
Figure BDA00003375991600771
[table 3]
Figure BDA00003375991600781
[table 4]
Figure BDA00003375991600791
By table 1～table 4 as can be known, can be confirmed by the evaluation result of embodiment 1 and comparative example 1, contain by use and have polyimide structures and polyamic acid structure as the polyimide of structural unit, multifunctional hydroxy-containing compounds and isocyanate compound; And the mol ratio of the isocyanate group that the hydroxyl that multifunctional hydroxy-containing compounds contains and isocyanate compound contain is the resin combination of hydroxyl/isocyanate base=0.5～1, can access warpage and fully be suppressed, has excellent stable on heating cured film.
In addition, by table 1 to table 3 as can be known, to the resin molding of sample 35, can control 120 ℃ to 220 ℃ viscosity and elastic part and the plasticity part of resin molding at the sample 1 of the resin combination that has used embodiment 1, so Resin Flow, through hole imbedibility, thermal shock patience are good.Therefore, under the situation of the manufacturing process that is used for wiring board, can take into account the imbedibility in through hole and prevent that resin combination from flowing out this 2 point from the end of wiring board.
About the resin combination of the 2nd embodiment of the present invention, describe with reference to following embodiment 2 to embodiment 12 and comparative example 2 to comparative example 6.Need to prove that following embodiment 2 to embodiment 12 is the resin combination of the 2nd mode.
＜reagent 〉
In embodiment and comparative example, employed reagent is as follows.Need to prove, at following embodiment 2 to embodiment 12 and comparative example 2 to comparative example 6 and table 5 and table 6, the abbreviation of the reagent that record is following.
(a) polyimide composition: BPDA (manufacturing of Mitsui Chemicals society), APB (trade(brand)name: APB-N, Mitsui Chemicals society makes), the diamines of general formula (5) expression: polyetheramine (trade(brand)name: polyetheramine D-400 (following simply be recited as " D-400 "), BASF society makes, m+n+p=6.1), JEFFAMINE (trade(brand)name: JEFFAMINE D-230 (following simply be recited as " D-230 "), Huntsman society makes, m+n+p=2.5), JEFFAMINE (trade(brand)name: JEFFAMINE XTJ-542 (following simply be recited as " XJT-400 "), Huntsman society makes, m+n+p=15), JEFFAMINE (trade(brand)name: JEFFAMINE D-2000, Huntsman society makes, m+n+p=33)
(b) 2 officials energy hydroxy-containing compounds: polycarbonate diol (trade(brand)name: DURANOL T5651 (following simply be recited as " T5651 "), chemistry society of Asahi Chemical Industry make), polycarbonate diol (trade(brand)name: DURANOL T4671 (following simply be recited as " T4671 "), chemistry society of Asahi Chemical Industry make)
(c-1) isocyanate compound: blocked isocyanate (trade(brand)name: DURANATE SBN-70D (following simply be recited as " SBN-70D "), chemistry society of Asahi Chemical Industry make), blocked isocyanate (trade(brand)name: DURANATE TPA-B80E (following simply be recited as " TPA-B80E "), chemistry society of Asahi Chemical Industry make)
(D) sensitizer 1 (compound with 2 two keys): EO modified bisphenol A dimethacrylate (trade(brand)name: BPE-500, Xin Zhong village chemical industry society make)
(D) sensitizer 2 (compound with two keys more than 3): TriMethylolPropane(TMP) PO modification triacrylate (trade(brand)name: Aronix M-310 (following simply be recited as " M-310 "), the synthetic society in East Asia make, are equivalent to have the compound of 3 two keys)
(E) Photoepolymerizationinitiater initiater: ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-ethanoyl oxime) (trade name: IRGACURE OXE-02, Ciba Japan society make)
(F) phosphorus compound: phosphazene compound (trade(brand)name: FP-300, volt see that society of pharmacy institute makes)
(other): toluene (using with the pure pharmaceutical worker of light society's manufacturing already, organic synthesis), gamma-butyrolactone (society makes with the pure pharmaceutical worker's industry of light), yellow soda ash (with the pure pharmaceutical worker of light society's manufacturing already)
＜weight-average molecular weight is measured 〉
Gel permeation chromatography (GPC) for as the weight-average molecular weight assay method utilizes following condition to measure.As solvent, use N, dinethylformamide (make with the pure pharmaceutical worker of light industry society, high performance liquid chromatography with), before mensuration, add the lithiumbromide monohydrate (make with the pure pharmaceutical worker's industry of light society, purity 99.5%) of 24.8mmol/L and the phosphoric acid of 63.2mmol/L (with the pure pharmaceutical worker's industry of light society manufacturing, high performance liquid chromatography with) and use.
Post: Shodex KD-806M (clear and electrician society makes)
Flow velocity: 1.0mL/ minute
Column temperature: 40 ℃
Pump: PU-2080Plus (manufacturing of JASCO society)
Detector: RI-2031Plus (RI: differential refractometer, JASCO society make)
UV-2075Plus (UV-VIS: UV, visible light absorptiometer, JASCO society make)
In addition, be used for calculating calibration curve use polystyrene standard (Dong Caoshe manufacturing) making of weight-average molecular weight.
＜determining film thickness 〉
The thickness of cured body uses film thickness gauge (manufacturing of Mitutoyo society, ID-C112B) to measure.
The manufacture method of＜photosensitive film 〉
The coating process of photosensitive polymer combination is undertaken by the skill in using a kitchen knife in cookery of scraping of using FILMCOATER (manufacturing of TESTER SANGYO society, PI1210).Above-mentioned photosensitive polymer combination is dropped to PET film (manufacturing of film society of Supreme Being people Du Pont, G2), and 150 μ m are coated with the gap.Use moisture eliminator (ESPEC society makes, SPHH-10l) with the above-mentioned film that is coated with 95 ℃ of dryings 12 minutes, obtain photosensitive film thus.
＜lamination condition 〉
Lamination uses vacuum press (name mechanism is done manufacturing) to carry out.Carry out lamination with 70 ℃ of press temperatures, pressing pressure 0.5MPa, the condition of 30 seconds press times.
＜development evaluation 〉
About the development evaluation, after coating foil lamination plate uses photosensitive film with above-mentioned lamination condition lamination, with 30-300mJ/cm 2Expose, then utilize 1 quality % aqueous sodium carbonate to carry out alkaline development and handle and utilize water to carry out rinsing, utilize the opticmicroscope evaluation pattern generating after the drying, development property evaluation thus.It is the circular pattern (100 μ m spacings at interval) of 100 μ m that mask uses diameter.By developing, will occur that copper face and residual film ratio are more than 90%, the situation of caving in of not observing pattern is designated as zero at unexposed, be more than 90% with residual film ratio but the situation of caving in of observing pattern is designated as △.
＜warpage after firing is measured 〉
With resulting photosensitive film with above-mentioned lamination condition lamination after KAPTON (registered trademark) (12 μ m) goes up, carry out firing in 2 hours at 180 ℃.It is square that this film is cut into 5cm, is that 5mm is designated as zero with interior situation with the end levitation height, will be designated as △ with interior situation for 5～10mm, and the situation that will have the above levitation height of 10mm is designated as *.
＜insulating reliability (IM patience) is estimated 〉
Insulating reliability is estimated following enforcement.Online empty than be on the comb type substrate of 20 μ m/20 μ m with behind the above-mentioned lamination condition lamination photosensitive film, expose and develop with above-mentioned condition, carry out firing in 2 hours at 180 ℃.Cable at film welding migration tstr carries out the insulating reliability test with following condition.
Insulation degradation evaluation system: SIR-12 (nanmu originally changes into society and makes)
IM chamber: EHS-211M (manufacturing of Espec society)
Temperature: 85 ℃
Humidity: 85%
Apply voltage: 20V
Application time: 1000 hours
Insulating resistance value: will be less than 1.0 * 10 6Ω is designated as *, with 1.0 * 10 6Ω～less than 1.0 * 10 7Ω is designated as △, with 1.0 * 10 7Ω～less than 1.0 * 10 8Ω is designated as zero, with 1.0 * 10 8Be designated as ◎ more than the Ω.
Outward appearance (dendrite): at opticmicroscope (manufacturing of ECLIPS LV100 Nikon society), see through the comb type substrate after observing the IM test under light, 200 times the condition, the situation of observing the generation of dendrite is designated as *, unobservable situation is designated as zero.
Outward appearance (expand and variable color): under the condition of 100 times of opticmicroscopes (manufacturings of ECLIPS LV100 Nikon society), the bright visual field, observe the comb type substrate after IM tests, the situation of observing the insulation expansion of tunicle and variable color is designated as *, the situation of only observing the expansion generation of insulation tunicle is designated as △, and the situation of not observing expansion and variable color is designated as zero.
＜polyimide (1) 〉
Under nitrogen atmosphere, in the removable flask that possesses Dean-Stark device and return channel, add gamma-butyrolactone (255g), toluene (51.0g), polyetheramine D-400 (86.8g (201.9mmol)), BPDA (120g (407.9mmol)), be warming up to 180 ℃, 180 ℃ of heated and stirred 1 hour.After removing the toluene as azeotropic solvent, be cooled to 40 ℃, then add APB-N (48.4g (165.7mmol)), stirred 4 hours at 40 ℃, obtain the solution of polyimide (1).The weight-average molecular weight of resulting polyimide (1) is listed in the table below 5.
＜polyimide (2) 〉
Under nitrogen atmosphere, in the removable flask that possesses Dean-Stark device and return channel, add gamma-butyrolactone (87.0g), toluene (17.0g), polyetheramine D-400 (5.00g (11.63mmol)), BPDA (30.0g (102.0mmol)), be warming up to 180 ℃, 180 ℃ of heated and stirred 1 hour.After removing the toluene as azeotropic solvent, be cooled to 40 ℃, then add APB-N (23.5g (80.39mmol)), stirred 4 hours at 40 ℃, obtain the solution of polyimide (2).The weight-average molecular weight of resulting polyimide (2) is listed in the table below 5.
＜polyimide (3) 〉
Under nitrogen atmosphere, in the removable flask that possesses Dean-Stark device and return channel, add gamma-butyrolactone (99.0g), toluene (20.0g), polyetheramine D-400 (32.0g (74.42mmol)), BPDA (30.0g (102.0mmol)), be warming up to 180 ℃, 180 ℃ of heated and stirred 1 hour.After removing the toluene as azeotropic solvent, be cooled to 40 ℃, then add APB-N (5.00g (17.10mmol)), stirred 4 hours at 40 ℃, obtain the solution of polyimide (3).The weight-average molecular weight of resulting polyimide (3) is listed in the table below 5.
＜polyimide (4) 〉
Under nitrogen atmosphere, in the removable flask that possesses Dean-Stark device and return channel, add gamma-butyrolactone (80.0g), toluene (16.0g), polyetheramine D-230 (16.8g (73.04mmol)), BPDA (30.0g (102.0mmol)), be warming up to 180 ℃, 180 ℃ of heated and stirred 1 hour.After removing the toluene as azeotropic solvent, be cooled to 40 ℃, (5.60g (19.16mmol) stirred 4 hours at 40 ℃, obtained the solution of polyimide (4) then to add APB-N.The weight-average molecular weight of resulting polyimide (4) is listed in the table below 5.
＜polyimide (5) 〉
Under nitrogen atmosphere, in the removable flask that possesses Dean-Stark device and return channel, add gamma-butyrolactone (107g), toluene (21.0g), JEFFAMINE XTJ-542 (25.7g (25.70mmol)), BPDA (30.0g (102.0mmol)), be warming up to 180 ℃, 180 ℃ of heated and stirred 1 hour.After removing the toluene as azeotropic solvent, be cooled to 40 ℃, (18.9g (64.65mmol) stirred 4 hours at 40 ℃, obtained the solution of polyimide (5) then to add APB-N.The weight-average molecular weight of resulting polyimide (5) is listed in the table below 5.
＜polyimide (6) 〉
Under nitrogen atmosphere, in the removable flask that possesses Dean-Stark device and return channel, add gamma-butyrolactone (120g), toluene (24.0g), JEFFAMINE D-2000 (27.4g (13.70mmol)), BPDA (30.0g (102.0mmol)), be warming up to 180 ℃, 180 ℃ of heated and stirred 1 hour.After removing the toluene as azeotropic solvent, be cooled to 40 ℃, (22.2g (75.94mmol) stirred 4 hours at 40 ℃, obtained the solution of polyimide (6) then to add APB-N.The weight-average molecular weight of resulting polyimide (6) is listed in the table below 5.
[embodiment 2]
With respect to polyimide (1) 100 mass parts, mix T5651 (6 mass parts), SBN-70D (6 mass parts), BPE-500 (40 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[embodiment 3]
With respect to polyimide (1) 100 mass parts, mix T4671 (6 mass parts), SBN-70D (6 mass parts), BPE-500 (40 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[embodiment 4]
With respect to polyimide (1) 100 mass parts, mix T5651 (6 mass parts), TPA-B80E (6 mass parts), BPE-500 (40 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[embodiment 5]
With respect to polyimide (1) 100 mass parts, mix T5651 (6 mass parts), SBN-70D (10 mass parts), BPE-500 (40 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[embodiment 6]
With respect to polyimide (1) 100 mass parts, mix T5651 (6 mass parts), SBN-70D (6 mass parts), BPE-500 (40 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[embodiment 7]
With respect to polyimide (1) 100 mass parts, mix T5651 (6 mass parts), SBN-70D (6 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[embodiment 8 to embodiment 12]
With respect to each 100 mass parts of polyimide (2)～(6), mix T5651 (6 mass parts), SBN-70D (6 mass parts), BPE-500 (40 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[comparative example 2]
With respect to polyimide (1) 100 mass parts, mix BPE-500 (40 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[comparative example 3]
With respect to polyimide (1) 100 mass parts, mix T5651 (6 mass parts), BPE-500 (40 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[comparative example 4]
With respect to polyimide (1) 100 mass parts, mix SBN-70D (6 mass parts), BPE-500 (40 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[comparative example 5]
With respect to polyimide (1) 100 mass parts, mix T5651 (6 mass parts), SBN-70D (15 mass parts), BPE-500 (40 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[comparative example 6]
With respect to polyimide (1) 100 mass parts, mix T5651 (15 mass parts), SBN-70D (6 mass parts), BPE-500 (40 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), the preparation photosensitive polymer combination.Resulting photosensitive polymer combination is utilized the aforesaid method dry filmization, obtain photosensitive film.Utilize aforesaid method, warpage, insulating reliability (IM patience) to the development of this photosensitive film, after firing are estimated.To the results are shown in following table 6.
[table 5]
? The diamines of general formula (5) expression (A+B)/(A+B+C) Weight-average molecular weight
Polyimide (1) D-400 0.55 23000
Polyimide (2) D-400 0.12 21000
Polyimide (3) D-400 0.81 25000
Polyimide (4) D-230 0.79 22000
Polyimide (5) XTJ-542 0.28 26000
Polyimide (6) D-2000 0.15 26000
[table 6]
Figure BDA00003375991600871
By the result shown in table 5, the table 6 as can be known, embodiment 2 to embodiment 12 compares to comparative example 6 with comparative example 2, and development, warpage, insulating reliability are good.Particularly in embodiment 2 to embodiment 12, under any situation of 0.10 ≦ (A+B)/(A+B+C) ≦ 0.85, all have development, warpage and insulating reliability.
Relative therewith, in the photosensitive composite that does not contain 2 officials energy hydroxy-containing compounds and isocyanate compound, produced warpage and dendrite (with reference to comparative example 2).In addition, under the situation that contains 2 officials energy hydroxy-containing compounds, in the photosensitive polymer combination that does not contain isocyanate compound, also observed improvement about warpage, but produced dendrite (with reference to comparative example 3).In addition, containing under the situation of isocyanate compound, in the photosensitive polymer combination that does not contain 2 officials energy hydroxy-containing compounds, also observed improvement about dendrite, but the result can produce warpage (with reference to comparative example 4).Think at these results: since do not contain to resultful 2 officials of the reduction of warpage can hydroxy-containing compounds, form the isocyanate compound of crosslinking structure with polyimide and two sense hydroxy-containing compounds, therefore produced warpage and dendrite.
In addition, under the situation that contains 2 officials energy hydroxy-containing compounds and isocyanate compound, the mol ratio of the isocyanate group of the hydroxyl of two sense hydroxy-containing compounds and isocyanate compound less than 0.5 photosensitive polymer combination in, also form the result's (with reference to comparative example 5) who produces warpage, in surpassing 1.0 photosensitive polymer combination, form the result's (with reference to comparative example 6) who produces dendrite.About these results, think owing to few to the ratio of the resultful 2 officials energy of the reduction of warpage hydroxy-containing compounds, thereby produce warpage, because the ratio of isocyanate compound is few, thereby can't forms sufficient crosslinking structure and produce dendrite with polyimide.
About the resin combination of the 3rd embodiment of the present invention, describe with reference to following embodiment 13 to embodiment 24 and comparative example 7, comparative example 8.Need to prove that following embodiment 13 to embodiment 24 is the resin combination of the 2nd mode.
＜reagent 〉
In embodiment and comparative example; silicone diamine (chemical industry society of SHIN-ETSU HANTOTAI manufacturing as employed reagent; KF-8010); 1; (Mitsui Chemicals society makes two (3-amino-benzene oxygen) benzene of 3-; APB-N); (IHARA CHEMICAL society makes polyoxygenated tetramethylene-two-para-amino benzoic acid ester; be called for short PMAB; following general formula (22)); 4; (Manac society makes the two O-phthalic acid dianhydrides of 4 '-oxygen; be called for short ODPA); 3; 3 '; 4; (Mitsui Chemicals society makes 4 '-biphenyl tetracarboxylic dianhydride; be called for short BPDA); (Daicel Chemical industry society makes pyromellitic acid dianhydride; be called for short PMDA); (new Japanese physics and chemistry society makes ethylene glycol bis (trimellitic acid monoesters acid anhydrides); RIKACID TMEG-100; be called for short TMEG); (big eight chemical societies make tricresyl phosphate (butoxyethyl group) ester; TBXP); (volt sees that society of pharmacy institute makes to phosphazene compound; Rabitle (registered trademark) FP-300; be called for short FP-300); ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-(Ciba Japan society makes 1-(O-ethanoyl oxime); trade name: IRGACURE OXE02; be called for short OXE-02); (Xin Zhong village chemical industry society makes two (4-(the methacryloxy five oxyethyl groups) phenyl) propane of 2,2-; trade name: BPE-500); (Xin Zhong village chemical industry society makes ethylene oxide (EO) modified bisphenol A dimethacrylate; trade name: BPE-500); (Xin Zhong village chemical industry society makes seven propylene glycol dimethacrylates; trade name: 9PG); (the synthetic society in East Asia makes tetramethylolmethane three/four (methyl) acrylate; trade name: Aronix M-306; be called for short M-306); (the synthetic society in East Asia makes TriMethylolPropane(TMP) EO modification triacrylate; trade name: Aronix M-350; be called for short M-350); (the synthetic society in East Asia makes TriMethylolPropane(TMP) PO modification triacrylate; trade name: Aronix M-310; be called for short M-310); (Xin Zhong village chemical industry society makes tetramethylol methane tetraacrylate; trade name: A-TMMT); (Xin Zhong village chemical industry society makes EO modified glycerol three (methyl) acrylate; A-GLY-9E (EO modification 9mol)); (chemistry society of Asahi Chemical Industry makes polycarbonate diol; DURANOL T5651); hexamethylene diisocyanate is that (chemistry society of Asahi Chemical Industry makes blocked isocyanate; DURANATE SBN-70D); (society makes toluene with the pure pharmaceutical worker's industry of light; organic synthesis is used); gamma-butyrolactone (society makes with the pure pharmaceutical worker's industry of light); triethylene glycol dimethyl ether (society makes with the pure pharmaceutical worker's industry of light); yellow soda ash (society makes with the pure pharmaceutical worker's industry of light) is not implemented special refining when being used for reaction.
General formula (22)
Figure BDA00003375991600891
＜weight-average molecular weight is measured 〉
Under the condition identical with the embodiment of above-mentioned the 2nd embodiment, measure.
＜photosensitive film manufacture method 〉
Similarly make with the embodiment of above-mentioned the 2nd embodiment.
＜lamination condition 〉
Similarly implement with the embodiment of above-mentioned the 2nd embodiment.
＜insulating reliability (HAST patience) is estimated 〉
Insulating reliability is estimated following enforcement.Online empty than be on the comb type substrate of 20 μ m/20 μ m with behind the above-mentioned lamination condition lamination photosensitive dry film, expose and develop with above-mentioned condition, carry out firing in 1 hour at 180 ℃.Cable at photosensitive dry film welding migration tstr carries out the insulating reliability test with following condition.
Insulation degradation evaluation system: SIR-12 (nanmu originally changes into society and makes)
HAST chamber: EHS-211M (manufacturing of Espec society)
Temperature: 110 ℃
Humidity: 85%
Apply voltage: 2V
Application time: 528 hours
Insulating resistance value: will be less than 1.0 * 10 6Ω is designated as *, with 1.0 * 10 6Ω～less than 1.0 * 10 7Ω is designated as △, with 1.0 * 10 7Ω～less than 1.0 * 10 8Ω is designated as zero, with 1.0 * 10 8Be designated as ◎ more than the Ω.
Outward appearance (dendrite): at opticmicroscope (manufacturing of ECLIPS LV100 Nikon society), see through the comb type substrate after observing the HAST test under light, 200 times the condition, the situation of observing the generation of dendrite is designated as *, unobservable situation is designated as zero.
Outward appearance (expand and variable color): under the condition of 100 times of opticmicroscopes (manufacturings of ECLIPS LV100 Nikon society), the bright visual field, observe the comb type substrate after HAST tests, observe diameter and be The expansion of the insulating coating of above size and/or the situation of variable color be designated as *, observe
Figure BDA00003375991600902
More than less than
Figure BDA00003375991600903
The expansion of insulating coating and/or the situation of variable color be designated as △, expand and variable color is
Figure BDA00003375991600904
Following situation is designated as zero.
＜warpage after firing is measured 〉
With resulting photosensitive dry film with above-mentioned lamination condition lamination after KAPTON (registered trademark) goes up, carry out firing in 1 hour at 180 ℃.It is square that photosensitive dry film is cut into 5cm, and the end levitation height is designated as ◎ less than the situation of 5mm, will float 5～be designated as zero less than the situation of 10mm, and the situation that will have the above levitation height of 10mm is designated as *.
＜resolving power evaluation 〉
Resolving power is estimated following enforcement.On the coating foil lamination plate with above-mentioned lamination condition lamination photosensitive dry film after, with 30-270mJ/cm 2Exposure.Then utilize 1 quality % aqueous sodium carbonate to carry out alkaline development and handle and utilize water to carry out rinsing, utilize opticmicroscope to estimate pattern after the drying.Mask uses the line sky of 50 μ m～100 μ m than (L/S) pattern.By developing, the residual film ratio of exposure portion (solidified portion) is 100%, has read the part that the copper face of unexposed (dissolving portion) occurs.The situation that can differentiate the L/S of 70 μ m is designated as ◎, and the situation that can differentiate the L/S pattern of 100 μ m is designated as zero, and the situation that can't differentiate 100 μ m is designated as *.
＜polyimide (7) 〉
Under nitrogen atmosphere, (KF-8010 (11.30g (13.78mmol)), ODPA (10.86g (35.00mmol)) were 120 ℃ of heated and stirred 1 hour to add triethylene glycol dimethyl ether (15g), gamma-butyrolactone (35g), toluene (20.0g), silicone diamine in removable flask.Dean-Stark device and return channel then is installed, 180 ℃ of heated and stirred 1 hour.Be cooled to 25 ℃ after removing the toluene as azeotropic solvent, (6.00g (20.52mmol) stirred 8 hours at 25 ℃, obtained the solution of polyimide (7) then to add APB-N.The weight-average molecular weight of resulting polyimide (7) is listed in the table below 7.
＜polyimide (8) 〉
Under nitrogen atmosphere, (KF-8010 (11.00g (13.41mmol)), BPDA (10.30g (35.00mmol)) were 120 ℃ of heated and stirred 1 hour to add triethylene glycol dimethyl ether (15g), gamma-butyrolactone (35g), toluene (20.0g), silicone diamine in removable flask.Dean-Stark device and return channel then is installed, 180 ℃ of heated and stirred 1 hour.Be cooled to 25 ℃ after removing the toluene as azeotropic solvent, (6.10g (20.87mmol) stirred 8 hours at 25 ℃, obtained the solution of polyimide (8) then to add APB-N.The weight-average molecular weight of resulting polyimide (8) is listed in the table below 7.
＜polyimide (9) 〉
Under nitrogen atmosphere, (KF-8010 (9.50g (11.59mmol)), PMDA (7.63g (35.00mmol)) were 120 ℃ of heated and stirred 1 hour to add triethylene glycol dimethyl ether (15g), gamma-butyrolactone (35g), toluene (20.0g), silicone diamine in removable flask.Dean-Stark device and return channel then is installed, 180 ℃ of heated and stirred 1 hour.Be cooled to 25 ℃ after removing the toluene as azeotropic solvent, (6.65g (22.75mmol) stirred 8 hours at 25 ℃, obtained the solution of polyimide (9) then to add APB-N.The weight-average molecular weight of resulting polyimide (9) is listed in the table below 7.
＜polyimide (10) 〉
Under nitrogen atmosphere, (KF-8010 (13.15g (16.04mmol)), TMEG (14.36g (35.00mmol)) were 120 ℃ of heated and stirred 1 hour to add triethylene glycol dimethyl ether (15g), gamma-butyrolactone (35g), toluene (20.0g), silicone diamine in removable flask.Dean-Stark device and return channel then is installed, 180 ℃ of heated and stirred 1 hour.Be cooled to 25 ℃ after removing the toluene as azeotropic solvent, (5.34g (18.27mmol) stirred 8 hours at 25 ℃, obtained the solution of polyimide (10) then to add APB-N.The weight-average molecular weight of resulting polyimide (10) is listed in the table below 7.
＜polyimide (11) 〉
Under nitrogen atmosphere, ((12.00g (9.69mmol)), ODPA (10.86g (35.00mmol)) were 120 ℃ of heated and stirred 1 hour to add triethylene glycol dimethyl ether (15g), gamma-butyrolactone (35g), toluene (20.0g), PMAB in removable flask.Dean-Stark device and return channel then is installed, 180 ℃ of heated and stirred 1 hour.Be cooled to 25 ℃ after removing the toluene as azeotropic solvent, (7.20g (24.63mmol) stirred 8 hours at 25 ℃, obtained the solution of polyimide (11) then to add APB-N.The weight-average molecular weight of resulting polyimide (11) is listed in the table below 7.
[embodiment 13～embodiment 15]
With respect to polyimide (7), polyimide (8), each 100 mass parts of polyimide (9), mix BPE-500 (20 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), the preparation photosensitive polymer combination.Utilize above-mentioned dry film manufacture method with resulting photosensitive polymer combination dry filmization, obtain photosensitive film.With above-mentioned lamination condition with this photosensitive film lamination in comb type substrate.Insulating reliability to resulting laminated film is estimated.To the results are shown in following table 8.In addition, in embodiment 13, embodiment 14, warpage is ◎, and resolving power is ◎, and in embodiment 15, warpage is zero, and resolving power is ◎.
[embodiment 16]
With respect to polyimide (7) 100 mass parts, mix BPE-500 (40 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), the preparation photosensitive polymer combination.Utilize the method identical with embodiment 13～embodiment 15 by resulting photosensitive polymer combination making laminated film, insulating reliability is estimated.To the results are shown in following table 8.In addition, warpage is ◎, resolving power is *.
[embodiment 17]
With respect to polyimide (7) 100 mass parts, mix M-310 (40 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), the preparation photosensitive polymer combination.Utilize the method identical with embodiment 13～embodiment 15 by resulting photosensitive polymer combination making laminated film, insulating reliability is estimated.To the results are shown in following table 8.In addition, warpage is zero, and resolving power is zero.
[embodiment 18]
With respect to polyimide (7) 100 mass parts, mix BPE-900 (20 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), the preparation photosensitive polymer combination.Utilize the method identical with embodiment 13～embodiment 15 by resulting photosensitive polymer combination making laminated film, insulating reliability is estimated.To the results are shown in following table 8.In addition, warpage is ◎, and resolving power is zero.
[embodiment 19]
With respect to polyimide (7) 100 mass parts, mix 9PG (20 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), the preparation photosensitive polymer combination.Utilize the method identical with embodiment 13～embodiment 15 by resulting photosensitive polymer combination making laminated film, insulating reliability is estimated.To the results are shown in following table 8.In addition, warpage is ◎, and resolving power is zero.
[embodiment 20]
With respect to polyimide (7) 100 mass parts, mix BPE-500 (20 mass parts), M-350 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), the preparation photosensitive polymer combination.Utilize the method identical with embodiment 13～embodiment 15 by resulting photosensitive polymer combination making laminated film, insulating reliability is estimated.To the results are shown in following table 8.In addition, warpage is ◎, and resolving power is ◎.
[embodiment 21]
With respect to polyimide (7) 100 mass parts, mix BPE-500 (20 mass parts), M-306 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), the preparation photosensitive polymer combination.Utilize the method identical with embodiment 13～embodiment 15 by resulting photosensitive polymer combination making laminated film, insulating reliability is estimated.To the results are shown in following table 8.In addition, warpage is ◎, and resolving power is ◎.
[embodiment 22]
With respect to polyimide (7) 100 mass parts, mix BPE-500 (20 mass parts), A-TMMT (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), the preparation photosensitive polymer combination.Utilize the method identical with embodiment 13～embodiment 15 by resulting photosensitive polymer combination making laminated film, insulating reliability is estimated.To the results are shown in following table 8.In addition, warpage is ◎, and resolving power is ◎.
[embodiment 23]
With respect to polyimide (7) 100 mass parts, mix BPE-500 (20 mass parts), A-GLY-9E (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), the preparation photosensitive polymer combination.Utilize the method identical with embodiment 13～embodiment 15 by resulting photosensitive polymer combination making laminated film, insulating reliability is estimated.To the results are shown in following table 8.In addition, warpage is ◎, and resolving power is ◎.
[embodiment 24]
With respect to polyimide (7) 100 mass parts, mix BPE-500 (20 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), T5651 (3 mass parts), SBN-70D (3 mass parts), the preparation photosensitive polymer combination.Utilize the method identical with embodiment 13～embodiment 15 by resulting photosensitive polymer combination making laminated film, insulating reliability is estimated.To the results are shown in following table 8.In addition, warpage is ◎, and resolving power is ◎.
[comparative example 7, comparative example 8]
With respect to polyimide (10), each 100 mass parts of polyimide (11), mix BPE-500 (20 mass parts), M-310 (20 mass parts), OXE-02 (1 mass parts), FP-300 (25 mass parts), TBXP (15 mass parts), the preparation photosensitive polymer combination.Utilize the method identical with embodiment 13～embodiment 15 by resulting photosensitive polymer combination making laminated film, insulating reliability is estimated.To the results are shown in following table 8.And the warpage of comparative example 7 and comparative example 8 is ◎, and resolving power is ◎.
[table 7]
Figure BDA00003375991600951
[table 8]
Figure BDA00003375991600961
By the result of table 7 and table 8 as can be known, in the embodiment 13～embodiment 24 that has used the photosensitive polymer combination that contains the polyamic acid structure shown in the polyimide structures shown in the above-mentioned general formula (7) and the above-mentioned general formula (8), compare insulating reliability (HAST patience) excellence with comparative example 8 with comparative example 7.In addition, embodiment 13 and embodiment 20 are compared as can be known with embodiment 22 and embodiment 23, and the insulating reliability (HAST patience) with resin combination of (methyl) acrylic compound of two keys more than 3 that contains the structure shown in the above-mentioned general formula (10) is better.
About the resin combination of the 4th embodiment of the present invention, describe with reference to following embodiment 25, embodiment 26 and comparative example 9～comparative example 11.Need to prove that following embodiment 25, embodiment 26 are the resin combination of the 2nd mode.
[embodiment 25]
In the present embodiment, as resin combination, use the phenol-modified silicone X-22-1821 (hydroxyl value 38mgKOH/g) that in the imidization rate is the varnish of 100% polyimide Z, added two tip type made of chemistry society of SHIN-ETSU HANTOTAI that can hydroxy-containing compounds as 2 officials, make to be 1 of oxazoline compound, the material of two (4, the 5-dihydro-2-oxazolyl) benzene (hereinafter referred to as BPO) of 3-and fire retardant A (with reference to embodiment 1).Use has added phenol-modified silicone X-22-18215 mass parts, BPO13 mass parts and the fire retardant A33 materials in parts by mass of two tip type of chemistry society of SHIN-ETSU HANTOTAI manufacturing with respect to polyimide Z100 mass parts.This resin combination is coated Copper Foil and 95 ℃ of dryings 12 minutes, obtained the resin molding that thickness is 30 μ m.This resin molding is used for the evaluation of alkali-soluble.And then with resin molding 180 ℃ the heating 60 minutes, obtain cured article.This cured article is used for alkali-proof evaluation.Below, the synthetic method of polyimide Z is described.
[polyimide Z]
Synthetic method to polyimide Z describes.At first, in three mouthfuls of removable flasks, nitrogen ingress pipe, thermometer are installed, possessed the spherical condensation tube of moisture seperating vale.Add triethylene glycol dimethyl ether 15g, gamma-butyrolactone 35g, toluene 20.0g, 4 under 25 ℃ of room temperatures, the two O-phthalic acid dianhydrides of 4 '-oxygen (Manac society makes, is called for short ODPA) 10.86g (35.00mmol) is stirred to evenly., be warming up to 80 ℃, add silicone diamine (chemical industry society of SHIN-ETSU HANTOTAI makes, is called for short KF-8010) 12.05g (14.7mmol), and then after stirring 0.5 hour, be warming up to 170 ℃, heated 4 hours thereafter.In the reaction, water and methylbenzene azeotropic that by-product is given birth to use the spherical condensation tube that possesses the moisture seperating vale to dewater under refluxing.After removing the living water of by-product, stop to reflux, toluene is all removed.After leaving standstill 12 hours, cooling under 25 ℃ of room temperatures, add 2,2 '-two (3-amino-4-hydroxyphenyl) HFC-236fa 7.56g (20.65mmol), gamma-butyrolactone 35g, toluene 20.0g.Stir after 0.5 hour, be warming up to 170 ℃, heated 4 hours.In the reaction, water and methylbenzene azeotropic that by-product is given birth to use the spherical condensation tube that possesses the moisture seperating vale to dewater under refluxing.After removing the living water of by-product, stop to reflux, toluene is all removed.Then with the strainer of 5 μ m with resultant pressure filtration, be 100% polyimide Z varnish thereby obtain the imidization rate.
[evaluation of warpage]
About the evaluation of warpage, estimate according to the rise of four jiaos of resin moldings.Specifically, under 23 ℃, the environment of humidity 50%, said sample 1 is cut into 5cm * 5cm, will measure as warpage with respect to the distance of floating at the angle of central part.It is good that warpage is that 10mm is evaluated as when following, is designated as zero, for 5mm is evaluated as when following better, is designated as ◎, for 15mm is designated as △ when following, is evaluated as badly when surpassing 15mm, be designated as *.
[evaluation of scolder patience]
About scolder patience, according to the JPCA-BM02 standard, the cured article that will cut into 3cm * 3cm is at 260 ℃ of dippings 60 seconds and estimating in solder bath.By visual inspection Check outward appearance, confirm to have or not variations such as distortion and dissolving vestige, the situation about find changing more than 90% of the total area is designated as zero, 50%～90% of the total area is found that situation about changing is designated as △, with the zone not finding to change less than 50% situation be designated as *.
[evaluation of alkali-soluble]
Resin molding be impregnated in 48 ℃, 3% aqueous sodium hydroxide solution, measure the dissolution rate of thickness, carry out the evaluation of alkali-soluble.Be that situation more than the 0.2 μ m/sec is designated as zero with the dissolution rate of thickness, will be designated as less than 0.2 μ m/sec *.
[alkali-proof evaluation]
With cured article dipping 1 minute in 48 ℃, 3% aqueous sodium hydroxide solution, measure the variation of the thickness before and after the dipping, carry out alkali-proof evaluation.Situation about being changed to below the 2 μ m is designated as zero, will be designated as above the situation of 2 μ m *.
[through hole imbedibility]
With the same condition of the embodiment 1 of above-mentioned the 1st embodiment under measure.
[cold shock testing]
With the same condition of the embodiment 1 of above-mentioned the 1st embodiment under measure.
[Resin Flow]
With the same condition of the embodiment 1 of above-mentioned the 1st embodiment under measure.
[embodiment 26]
In the present embodiment, as resin combination, use with respect to polyimide Z100 mass parts added two tip type made of chemistry society of SHIN-ETSU HANTOTAI that can hydroxy-containing compounds as 2 officials phenol-modified silicone X-22-182110 mass parts, make BPO20 mass parts and fire retardant A33 materials in parts by mass as the oxazoline compound.In addition make resin molding, cured article and evaluation similarly to Example 25.
[comparative example 9]
In the present embodiment, as resin combination, use with respect to polyimide Z100 mass parts not add 2 officials energy hydroxy-containing compounds and added fire retardant A33 materials in parts by mass.In addition make resin molding, cured article and evaluation similarly to Example 25.
[comparative example 10]
In the present embodiment, as resin combination, do not use polyimide Z, use the phenol-modified silicone X-22-182110 mass parts that added two tip type made of chemistry society of SHIN-ETSU HANTOTAI that can hydroxy-containing compounds as 2 officials, make BPO20 mass parts and fire retardant A33 materials in parts by mass as the oxazoline compound.In addition make resin molding, cured article and evaluation similarly to Example 25.
[comparative example 11]
In the present embodiment, as resin combination, use the phenol-modified silicone X-22-182110 mass parts and the fire retardant A33 materials in parts by mass that have added two tip type made of chemistry society of SHIN-ETSU HANTOTAI that can hydroxy-containing compounds as 2 officials with respect to polyimide Z100 mass parts.In addition make resin molding, cured article and evaluation similarly to Example 25.
The evaluation result of embodiment 25, embodiment 26 and comparative example 9～comparative example 11 is listed in the table below 9.By following table 9 as can be known, used the resin molding of the resin combination of embodiment 25, embodiment 26 to demonstrate alkali-soluble, cured article demonstrates alkali resistance simultaneously, and then warpage is low, scolder patience excellence, has obtained the effect same with the resin combination of above-mentioned other embodiment.On the other hand, by comparative example 9～comparative example 11 as can be known, do not comprise polyimide, 2 officials can hydroxy-containing compounds and the oxazoline compound in any one situation under, the evaluation of scolder patience and warpage etc. worsens.
[table 9]
Figure BDA00003375991601001
Need to prove that the present invention is not limited to above-mentioned embodiment, can carry out various changes and implement.In the above-mentioned embodiment, about size shown in the drawings and shape etc., be not limited to this, can suitable change in the scope of performance effect of the present invention.In addition, only otherwise break away from the scope of purpose of the present invention, then can suit change and implement.
Industrial applicibility
The present invention has the effect that can realize following resin combination: the abundant reduction of warpage and excellent thermotolerance when this resin combination can be realized solidifying; particularly, can suit as surface protection film, interlayer dielectric, bonding sheet, conductor package substrate, the protective layer of circuit substrate, use in printed circuit board protection insulating film, the flexible printed board protection insulating film of semiconductor element.
The Japanese Patent Application 2011-160730 that the Japanese Patent Application 2011-107290 that the Japanese Patent Application 2011-062186 that submits in the Japanese Patent Application 2011-007862 that the application submitted to based on January 18th, 2011, on March 22nd, 2011, on May 12nd, 2011 submit to and on July 22nd, 2011 submit to.These contents all comprise in this application.

Claims (33)

1. resin combination is characterized in that it contains:
(A) macromolecular compound;
(B) multifunctional hydroxy-containing compounds has 2 above hydroxyls; With
(C) multifunctional cross-linked compound has the bridging property functional group more than 2 that forms cross-link bond between itself and described macromolecular compound and/or described multifunctional hydroxy-containing compounds,
Described multifunctional cross-linked compound can and described macromolecular compound and/or described multifunctional hydroxy-containing compounds between form three-dimensional cross-linked.
2. resin combination as claimed in claim 1 is characterized in that, described macromolecular compound has imide and/or amide group, described three-dimensional cross-linked C=O base and/or the NH base of comprising.
3. as claim 1 or the described resin combination of claim 2, it is characterized in that described multifunctional hydroxy-containing compounds and/or described multifunctional cross-linked compound are more than 3 official's energy.
4. as each described resin combination of claim 1～claim 3, it is characterized in that described macromolecular compound has hydroxyl and/or carboxyl.
5. as each described resin combination of claim 1～claim 4, it is characterized in that, as described multifunctional hydroxy-containing compounds, comprise and be selected from least a in two terminal phenol-modified silicone, polybutadiene polyol, hydrogenated butadiene polymer polyvalent alcohol and the polycarbonate polyol.
6. as each described resin combination of claim 1～claim 5, it is characterized in that described multifunctional hydroxy-containing compounds contains aliphatic structure.
7. as each described resin combination of claim 1～claim 6, it is characterized in that described multifunctional hydroxy-containing compounds is polycarbonate polyol.
8. as each described resin combination of claim 1～claim 7, it is characterized in that, as described multifunctional cross-linked compound, comprise the polyfunctional isocyanate's compound with 2 above isocyanate group.
9. as each described resin combination of claim 1～claim 8, it is characterized in that described multifunctional cross-linked compound comprises the blocked isocyanate base more than 2.
10. as each described resin combination of claim 1～claim 9, it is characterized in that the mol ratio of the bridging property functional group that the hydroxyl that described multifunctional hydroxy-containing compounds contains and described multifunctional cross-linked compound contain is hydroxyl/bridging property functional group=0.5～1.
11. each the described resin combination as claim 1～claim 10 is characterized in that, with respect to described macromolecular compound 100 mass parts, the content of described multifunctional hydroxy-containing compounds is 5 mass parts～60 mass parts.
12. each the described resin combination as claim 1～claim 11 is characterized in that, with respect to described macromolecular compound 100 mass parts, the content of described multifunctional cross-linked compound is 5 mass parts～60 mass parts.
13. each the described resin combination as claim 1～claim 12 is characterized in that the number-average molecular weight of described multifunctional hydroxy-containing compounds is 500～3000.
14. each the described resin combination as claim 1～claim 13 is characterized in that, described macromolecular compound has the repeating structure of following general formula (1) expression,
General formula (1)
Figure FDA00003375991500021
In the formula (1), Y 1The organic group of expression divalent, Z 1The organic group of representing 4 valencys, a are represented 1～50 integer.
15. each the described resin combination as claim 1～claim 14 is characterized in that described macromolecular compound is polyimide.
16. each the described resin combination as claim 1～claim 15 is characterized in that, described macromolecular compound has the repeating structure of following general formula (2) expression,
General formula (2)
Figure FDA00003375991500022
In the formula (2), Z 1And Z 2The organic group of representing 4 valencys, Y 1, Y 2, Y 3, Y 4And Y 5Represent that independently of one another carbonatoms is that 1～carbonatoms is 5 alkylidene group, have or do not have side chain, b, c and d represent 1～50 integer independently of one another.
17. each described resin combination as claim 1～claim 16, it is characterized in that, described macromolecular compound has the polyamic acid structure of the polyimide structures of following general formula (3) expression and following general formula (4) expression respectively as repeated structural unit
General formula (3)
Figure FDA00003375991500031
General formula (4)
Figure FDA00003375991500032
In formula (3) and the formula (4), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency, R 3, R 6, R 9, R 12And R 15Represent that independently of one another carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, m, n, p represent the integer below 100 more than 0, R independently of one another 16The organic group of representing 4 valencys, R 17The expression carbonatoms is that 1～carbonatoms is the organic group of 90 divalent.
18. resin combination as claimed in claim 17 is characterized in that, as two amine components of the polyimide that constitutes described general formula (3) expression, comprises the diamines of following general formula (5) expression,
General formula (5)
In the formula (5), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency, R 3, R 6, R 9, R 12And R 15Represent that independently of one another carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, m, n, p represent the integer below 30 more than 0 independently of one another, satisfy 1 ≦ (m+n+p) ≦ 30.
19. each the described resin combination as claim 1～claim 18 is characterized in that, described macromolecular compound has the structure of following general formula (6) expression as repeating unit,
General formula (6)
In the formula (6), R 1, R 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13And R 14Represent that independently of one another hydrogen atom or carbonatoms are that 1～carbonatoms is the organic group of 20 1 valency, R 3, R 6, R 9, R 12And R 15The expression carbonatoms is that 1～carbonatoms is the organic group of 20 4 valencys, and m, n, p represent the integer below 30 more than 0, R independently of one another 16The organic group of representing 4 valencys, R 17The expression carbonatoms is that 1～carbonatoms is the organic group of 90 divalent, and A, B, C represent the mole % of each unit, satisfy 0.10 ≦ (A+B)/(A+B+C) ≦ 0.85.
20. each the described resin combination as claim 1～claim 19 is characterized in that, described macromolecular compound has the polyamic acid structure of the polyimide structures of following general formula (7) expression and following general formula (8) expression as structural unit,
General formula (7)
General formula (8)
Figure FDA00003375991500042
In formula (7) and the formula (8), Z 3And Z 4Be the organic group from the tetracarboxylic dianhydride's of following general formula (9) expression 4 valencys, identical or different separately; R 18The expression carbonatoms is that 1～carbonatoms is the organic group of 30 divalent, R 19The expression carbonatoms is that 1～carbonatoms is the organic group of 30 1 valency, and e represents the integer below 20 more than 1,
General formula (9)
Figure FDA00003375991500043
21. each the described resin combination as claim 1～claim 20 is characterized in that it contains:
(D) have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound and
(E) Photoepolymerizationinitiater initiater.
22. resin combination as claimed in claim 21 is characterized in that, as described have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound, comprise (methyl) acrylic compound with two keys more than 3.
23. resin combination as claimed in claim 22 is characterized in that, as described (methyl) acrylic compound with two keys more than 3, comprises the compound of following general formula (10) expression,
General formula (10)
Figure FDA00003375991500051
In the formula (10), R 20Expression hydrogen atom or methyl, a plurality of E represent that independently of one another carbonatoms is that 2～carbonatoms is 5 alkylidene group, identical or different separately, f is 1～10 integer.
24. each described resin combination as claim 21～claim 23, it is characterized in that, as described have more than 2 can photopolymerisable unsaturated double-bond (methyl) acrylic compound, comprise (methyl) acrylic compound with 2 two keys and have (methyl) acrylic compound of two keys more than 3.
25. each the described resin combination as claim 1～claim 24 is characterized in that it contains (F) phosphorus compound.
26. resin combination as claimed in claim 25 is characterized in that, as described phosphorus compound, comprises phosphate compound and/or phosphazene compound.
27. a resin combination is characterized in that, in 85 ℃ of temperature, humidity 85%, 1000 hours insulating reliability test, layer insulation resistance is 10 9More than the Ω, 120 ℃～220 ℃ viscosity is 5000PaS～100000PaS,
It is plasticity part more than 50% less than 20% elastic part and elongation that this resin combination has elongation, and the thickness of interlayer insulating film is below the 40 μ m.
28. a cured article is characterized in that, it obtained 160 ℃～200 ℃ heating after 5 minutes～60 minutes 100 ℃～130 ℃ heating by each the described resin combination with claim 1～claim 27 in 15 minutes～60 minutes again.
29. a resin molding is characterized in that it possesses:
Base material and
Be arranged at each described resin combination of the claim 1～claim 27 on the described base material.
30. resin molding as claimed in claim 29 is characterized in that, described base material is carrier film.
31. as claim 29 or the described resin molding of claim 30, it is characterized in that it possesses the mulch film that is arranged on the described resin combination.
32. each the described resin molding as claim 29～claim 31 is characterized in that described base material is Copper Foil.
33. a wiring board is characterized in that it possesses:
Have distribution base material and
Each described resin combination of the claim 1～claim 27 that arranges in the mode that covers described distribution.
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