CN101107291A - Polyimide resin, polyimide film, and polyimide laminate - Google Patents
Polyimide resin, polyimide film, and polyimide laminate Download PDFInfo
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- CN101107291A CN101107291A CNA2006800027760A CN200680002776A CN101107291A CN 101107291 A CN101107291 A CN 101107291A CN A2006800027760 A CNA2006800027760 A CN A2006800027760A CN 200680002776 A CN200680002776 A CN 200680002776A CN 101107291 A CN101107291 A CN 101107291A
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Abstract
Disclosed is a polyimide resin composed of a repeating unit represented by the formula (1) below, or alternatively a repeating unit represented by the formula (1) below and at least one repeating unit represented by the formula (2) below (wherein X is as defined in the description). [Chemical formula 1] [Chemical formula 2] The polyimide resin is good in thermoplasticity, solubility in solvents and heat resistance, while exhibiting low water absorption and excellent adhesiveness. This polyimide resin is useful as a material for the adhesive layer in a metal-clad laminate which includes an insulating base, a metal layer and an adhesive layer arranged between the insulating base and the metal layer.
Description
Technical field
The present invention relates to show polyimide resin, this polyimide resin film of good thermotolerance, solvent soluble and thermoplasticity and low water absorbable and the clad with metal foil lamination body that has used the binding agent that forms by this polyimide resin.This clad with metal foil lamination body can be processed into printed circuit board, face heating element, electromagnetic shielding material, flat cable etc.
Background technology
Clad with metal foil lamination body can utilize binding agent or cohesiveness film to bond insulating substrate and metal level and make.For example, insulating substrate and the metal level that is formed by aromatic series quasi-polyimide resin film utilizes cohesiveness film bonding to form the clad with metal foil lamination body (with reference to patent documentation 1) of 3-tier architecture.
Mainly used binding agent or the cohesiveness film that forms by epoxies or acrylic resin as binding agent or cohesiveness film in the past.But these resins are owing to poor heat resistance, and the thermotolerance of bonding back product is insufficient, to processing conditions, working conditions generation restriction thereafter.
For this reason, wish to obtain good binding agent of thermotolerance and cohesiveness film.The solution that discloses polyimide or polyamic acid at present is coated on the insulating substrate, removes then and desolvates, and according to circumstances carry out imidization and handle, and forms the method for the tack coat of thermo-compressed; In addition, also disclose solution with polyimide or polyamic acid and be coated on the sheet glass etc., removed then and desolvate, and according to circumstances carry out imidization and handle, formed the method for thermo-compressed film; And, the method (with reference to patent documentation 2,3) of bonded thing such as thermo-compressed metal level on the tack coat that forms like this, cohesiveness film.Above-mentioned tack coat formation method is divided into the method for using polyimide resin solution and the method for using polyamic acid solution substantially.
In using the method for polyamic acid solution, be coated in polyamic acid solution on insulating substrate or the sheet glass after, in order to form tack coat or cohesiveness film, need carry out imidization technology surpassing under 300 ℃ the high temperature.The thermotolerance of the clad with metal foil lamination body that omits imidization technology and form is very low.In using the method for polyimide solution, as long as the coating back is with solvent evaporates, can form tack coat or cohesiveness film under the low temperature till about 200 ℃.Therefore, use the method for polyimide solution to help preparing high heat resistance clad with metal foil lamination body more.The tack coat great majority that formed by all aromatic polyimide resin in the past utilize polyamic acid solution to form.In order to obtain polyimide resin solution, polyimide resin must be the solvent soluble polyimide resin.
In clad with metal foil lamination body, the residual volatile component that is configured in the tack coat between insulating substrate and the metal level more for a long time, will produce albefaction, expansion, foaming of tack coat etc. when under the high temperature more than 250 ℃, carrying out soldering tin technique, the compactness of insulating substrate and metal level be badly damaged (with reference to patent documentation 4).The moisture that the residue volatile component of this tack coat can enumerate that imidization, solvent when forming tack coat or cohesiveness film removed the moisture do not removed in the technology and solvent, absorb during the aqueous solution dipping of the moisture that absorbs from the preparation environment and etch process etc.What wherein become problem especially is moisture.For addressing the above problem, the water-intake rate that hope will become the moisture content index of imidization reduces.
In addition, disclose from 1,2,4, but contained 1,2,4 in the molecular backbone chain of the heat fusing that obtains in 5-hexanaphthene tetracarboxylic dianhydride and the reactive derivatives thereof, the polyimide resin (with reference to patent documentation 6) of 5-hexanaphthene tetracarboxylic acid skeleton.In the embodiment 1 of this patent, with 1,2,4,5-hexanaphthene tetracarboxylic dianhydride and reactive derivatives thereof and diaminodiphenyl-methane reaction form amido acid, its coating post-heating is carried out imidization, and further being heated press molding, to obtain second-order transition temperature be 304 ℃ transparent and xanchromatic polyimide resin film.In addition, disclose from the polyimide resin solution that utilizes diaminodiphenyl oxide to obtain in the patent documentation 5, obtained second-order transition temperature and be the transparent and painted few polyimide resin film more than 300 ℃.
Above-mentionedly contain 1,2,4, the polyimide resin ratio of 5-hexanaphthene tetracarboxylic acid skeleton is easier to high molecularization, obtains the flexible thin film easily, and also fully big to the solubleness of solvent, so favourable aspect the shaping processing of film.In addition, by applying the tack coat that easy formation flexible has thickness sufficient and weather resistance, so very useful.
But, patent documentation 6 described polyimide resin films are identical with previous methods to be formed through pyritous imide technology, so film can be painted, and patent documentation 5 and 6 described polyimide resin films in addition, its water-intake rate height, moisture absorption size poor stability.
Patent documentation 1: the spy opens clear 55-91895 communique
Patent documentation 2: the spy opens flat 5-32950 communique
Patent documentation 3: the spy opens flat 5-59344 communique
Patent documentation 4: the spy opens the 2001-329246 communique
Patent documentation 5: the spy opens the 2003-168800 communique
Patent documentation 6: the U.S. speciallys permit specification sheets No. 3639343
Summary of the invention
The present invention seeks to solve the problem of all aromatic polyimide resin that in the past was used for tack coat, the clad with metal foil lamination body that polyimide resin of the good low water absorbable of thermoplasticity, solvent soluble, thermotolerance and cohesiveness and preparation method thereof is provided, contains the film of this polyimide resin and contain the tack coat that forms by this polyimide resin.
Present inventors further investigate for addressing the above problem, and it found that the polyimide resin that is made of specific repeating unit has good thermoplastic, cohesiveness, solvent soluble and thermotolerance, and water-absorbent is low.And, by and with the compound with ad hoc structure or particular functional group as two amine components or by with the viscosity limitation of polyimide resin at specified range, can improve cohesiveness to metal level and insulating substrate.Finish the present invention according to above-mentioned discovery.
Just, the invention provides the polyimide resin that repeating unit of being represented by following general formula (1) or at least a repeating unit of being represented by the repeating unit and the following general formula (2) of described general formula (1) expression form, the ratio of the repeating unit of described general formula (1) is for always repeating unitary 50 moles more than the %, and utilizing the N-N-methyl-2-2-pyrrolidone N-solution of 0.5g/dL is 0.3～2dL/g in the logarithm viscosities il of the above-mentioned polyimide resin of 30 ℃ of mensuration.
[changing 1]
[changing 2]
(in the formula, X is that carbonatoms is that 2～39 aliphatic divalent group, carbonatoms are that 3～39 divalence alicyclic group, carbonatoms are 6～39 divalence aromatic group or by their divalent group that is combined to form, the main chain of X also can have be selected from by-O-,-SO
2-,-CH
2-,-C (CH
3)
2-,-OSi (CH
3)
2-,-C
2H
4O-and-at least a conjugated group in the group that S-formed, X also can have at least a functional group that is selected from the group of being made up of carboxyl, hydroxyl or carbonyl, when having this functional group, the concentration F of functional group is above zero and below the 1meq/g polyimide resin.)
And the present invention also provides the preparation method of above-mentioned polyimide resin.
In addition, the present invention also provides and has comprised above-mentioned polyimide resin behind casting on the support, evaporates the preparation method of the polyimide resin film of the technology of removing organic solvent.
The present invention also provides the clad with metal foil lamination body of the tack coat that contains insulating substrate, metal level and dispose between above-mentioned insulating substrate and metal level, above-mentioned tack coat is formed by above-mentioned polyimide resin.
Embodiment
Polyimide resin of the present invention (following table is shown polyimide A) is by the repeating unit of following general formula (1) expression or the polyimide resin that formed by at least a repeating unit of the repeating unit of described general formula (1) expression and following general formula (2) expression, the ratio of the repeating unit of described general formula (1) is for always repeating unitary 50 moles more than the %, be preferably 70 moles more than the %, more preferably 80 moles of % above (comprising 100 moles of % respectively).Polyimide A can be any one of segmented copolymer or a random copolymers.
[changing 3]
[changing 4]
X in the above-mentioned general formula (2) is different with following formula (3), is that carbonatoms is that 2～39 aliphatic divalent group, carbonatoms are that 3～39 divalence alicyclic group, carbonatoms are 6～39 divalence aromatic group or by their divalent group that is combined to form.The main chain of X also can have be selected from by-O-,-SO
2-,-CH
2-,-C (CH
3)
2-,-OSi (CH
3)
2-,-C
2H
4O-and-at least a conjugated group in the group that S-formed.X also can have at least a functional group that is selected from the group of being made up of carboxyl, hydroxyl or carbonyl (containing) on the main chain of X.X specifically can enumerate, the aliphatic divalent group of polyalkylene, polyoxy alkylidene, benzene (support) dimethyl and their alkyl substituent, halogen substituent, carboxyl substituted thing and hydroxyl substituent etc.; From hexanaphthene, double-hexyl methane, dimethyl cyclohexane, isophorone, norbornane and deutero-divalence alicyclic groups such as their alkyl substituent, halogen substituent, carboxyl substituted thing and hydroxyl substituent; From benzene, naphthalene, biphenyl, ditan, phenyl ether, sulfobenzide, benzophenone and deutero-divalence aromatic groups such as their alkyl substituent, halogen substituent, carboxyl substituted thing and hydroxyl substituent.Balance for the various characteristics that keeps tack coat improves cohesive strength simultaneously, and X is preferably a penylene base or a penylene dimethyl.
[changing 5]
When X had above-mentioned functional group, the functional group concentration F that represents with the milliequivalent of the polyimide resin of every 1g surpassed zero and below the 1meq/g polyimide resin, was preferably to surpass zero and below the 0.6meq/g polyimide resin.Functional group concentration F can the raw material add-on when synthetic easily obtain.When functional group concentration F was excessive, though cohesiveness improves, it is big that water-absorbent becomes, thus surpass 1 not preferred, in the time obtaining required cohesiveness, as far as possible little of well in above-mentioned scope.
Because polyimide A uses as solution, so its molecular weight is preferably with viscosity, particularly be expressed as with logarithm viscosity.The logarithm viscosities il of polyimide A (the N-N-methyl-2-2-pyrrolidone N-solution that utilizes 0.5g/dL is 30 ℃ of mensuration) is 0.3～2dL/g.When not enough 0.3dL/g, the weakened of polyimide resin itself, the clad with metal foil lamination body that can not obtain having abundant stripping strength.When surpassing 2.0dL/g, its solution (lacquer) viscosity height is difficult to coating, needs dilution significantly, is difficult to operation.Balance for the various characteristics that keeps tack coat improves cohesive strength simultaneously, and the logarithm viscosities il is preferably 0.3～1dL/g.
In general, the molecular end of polyimide A is amino, carboxyl or acid anhydride.By these molecular end being had the compound reaction of acid anhydride, amino, can reduce the functional group of molecular end as much as possible, perhaps can introduce functional group or the substituting groups beyond these such as amino, carboxyl consciously in molecular end.In order to reduce water-intake rate, also can introduce the little substituting group of polarity (substituting group that does not have functional group) in molecular end.Utilize the water-intake rate of the polyimide A of aftermentioned method mensuration to be preferably below 2.5%.The industrial water-intake rate minimum value that can reach is about 1% usually.
Polyimide A will be selected from 1,2,4,5-hexanaphthene tetracarboxylic acid, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (HPMDA) and 1,2,4, at least a tetracarboxylic acid composition (Y) in the 5-hexanaphthene tetracarboxylic ester class isoreactivity derivative be selected from least a two amine components (Z) in diamines and the reactive derivatives thereof and react and obtain.Tetracarboxylic acid composition (Y) is preferably HPMDA.Tetracarboxylic acid composition (Y) and two amine components (Z) comprise isomer.
Two amine components (Z) can be enumerated diamines, vulcabond, diamino disilane class etc., are preferably diamines.Two amine components (two amine components (Z1)) that are used to form the repeating unit of above-mentioned general formula (1) are 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) and the reactive derivatives thereof of 2-, and two amine components (two amine components (Z2)) that are used to form the repeating unit of above-mentioned general formula (2) are NH
2-X-NH
2(X is same as described above) and reactive derivatives thereof.
Two amine components (Z2) can be the reactive derivatives of aromatic diamine, aliphatie diamine, alicyclic diamine, above-mentioned diamines and their mixture." aromatic diamine " among the present invention is meant the amino diamines that directly is connected on the aromatic ring, can contain aliphatic group, alicyclic group, aromatic group and other substituting group in the part of its structure." aliphatie diamine " is meant the amino diamines that directly is connected on the aliphatic group, can contain aliphatic group, alicyclic group, aromatic group, other substituting group in the part of its structure." alicyclic diamine " is meant the amino diamines that directly is connected on the alicyclic group, can contain aliphatic group, alicyclic group, aromatic group, other substituting group in the part of its structure.For example 1, (mphenylenediamine is because amino directly is connected on the aromatic ring (phenyl ring) MPD) to the 3-phenylenediamine, and institute thinks that aromatic diamine, m-xylene diamine (MXDA) are because amino directly is connected on the fatty group (methylene radical), and institute thinks aliphatie diamine.
In general, when tetracarboxylic dianhydride and aliphatie diamine or alicyclic diamine react, form stable salt as the polyamic acid of intermediate product and amino, so be difficult to obtain the high molecular polyimide from aliphatie diamine or alicyclic diamine.Therefore, need to use solvability to salt, for example cresols etc. than higher solvent.But, using 1,2,4,5-hexanaphthene tetracarboxylic dianhydride is during as the tetracarboxylic dianhydride, and polyamic acid forms more weak bonded salt with amino from aliphatie diamine or alicyclic diamine, so than being easier to carry out imide reaction, implement the polymer quantification easily.
Aliphatie diamine can be enumerated, for example two (3-aminopropyl) ethers of Edamine, hexamethylene diamine, polyoxyethylene glycol, two (3-aminopropyl) ethers, 1 of polypropylene glycol, 3-, two (amino methyl) hexanaphthene, 1, two (amino methyl) hexanaphthenes of 4-, p dimethylamine, m-xylene diamine, siloxane diamine class etc.
Alicyclic diamine can be enumerated, and for example 4,4 '-diamino-dicyclohexyl methane, isophorone diamine, norbornane diamines etc.
Aromatic diamine can be enumerated, for example 1, the 4-phenylenediamine, 1, the 3-phenylenediamine, 2, the 4-tolylene diamine, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl-methane, 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-, α, α '-two (4-aminophenyl)-1,4-diisopropyl benzene, α, α '-two (3-aminophenyl)-1, the 4-diisopropyl benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-diaminodiphenylsulfone(DDS), two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, 2, the 6-diaminonaphthalene, 1,5-diaminonaphthalene etc.
Diamines with above-mentioned functional group can be enumerated, and for example 3,3 '-dicarboxyl-4,4 '-diaminodiphenyl-methane, 3,5-diamino M-nitro benzoic acid, 3,3 '-dihydroxyl-4,4 '-benzidine, 2,4-diaminophenol, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone.Be preferably 3 especially, 3 '-dicarboxyl-4,4 '-diaminodiphenyl-methane (MBAA), 3,5-diamino M-nitro benzoic acid (DBA), 3,3 '-dihydroxyl-4,4 '-benzidine (HAB), 4,4 '-diaminobenzophenone (4,4 '-DBP).
The diamines, MPD or the MXDA that have functional group by use are as two amine components (Z2), perhaps the N-N-methyl-2-2-pyrrolidone N-by will utilizing 0.5g/dL is controlled at the scope of 0.3～2dL/g in the logarithm viscosities il of the polyimide resin of 30 ℃ of mensuration, can improve the cohesive force of polyimide resin.
Polyimide A preferably uses 0.66～1.5 mole with above-mentioned tetracarboxylic acid composition (Y), more preferably 0.9～1.1 mole, further preferred 0.97～1.03 mole, make with 1 mole above-mentioned two amine components (Z) (two amine components (Z1) or two amine components (Z1)+two amine components (Z2)) reaction.The diamines that use has an above-mentioned functional group is during as diamines (Z2), its usage quantity is adjusted to make above-mentioned functional group concentration F be below the 1meq/g polyimide resin.
Usage ratio, temperature of reaction and reaction times by regulating raw material for example, the use that end stops agent whether with at least one conditions of usage quantity, catalytic amount etc., can prepare polyimide A with the logarithm viscosities il in the above-mentioned scope.The adjusting of above-mentioned condition is by ready reaction etc., and those skilled in the art can implement easily.For example, when regulating the logarithm viscosities il according to the mol ratio of above-mentioned tetracarboxylic acid composition (Y) and above-mentioned two amine components (Z) and reaction times, above-mentioned mol ratio approaches 1 more, in addition the reaction times long more, the logarithm viscosities il is big more in above-mentioned scope.Above-mentioned mol ratio in 0.66～1.5 scope more away from 1, in addition the reaction times short more, the logarithm viscosities il is more little in above-mentioned scope.In the solution polymerization process, obtain the reaction conditionss such as viscosity, reaction times etc. of reaction soln in advance and,, determine reaction end, can prepare the polyimide A that specifies the logarithm viscosities il thus according to this relation corresponding to the relation between the logarithm viscosity of these conditions.Reaction times is preferably 2～12 hours, and temperature of reaction is preferably 180～205 ℃.
Polyimide A is mixed with organic solvent solution usually.
Organic solvent is not particularly limited, can use N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethyl acetamide, N, dinethylformamide, N, N-diethylformamide, N-methyl caprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide (DMSO), meta-cresol, phenol, para-chlorophenol, 2-chloro-4-hydroxytoluene, diglyme, triglyme, tetraethylene glycol dimethyl ether, dioxane, gamma-butyrolactone, two oxa-s, penta ring, pimelinketone, cyclopentanone etc. also can be used in combination.But, when considering the performance by the polyimide varnish of polyimide A and solvent composition, preferably N-N-methyl-2-2-pyrrolidone N-(NMP), N,N-dimethylacetamide (DMAC), gamma-butyrolactone (GBL) are used singly or in combination.The usage quantity of organic solvent be for can make the polyimide A concentration in the organic solvent solution that obtains be preferably 1～50 weight %, more preferably 5～40 weight %.In addition, when utilizing solution polymerization to prepare, can use Weak solvents such as hexane, heptane, benzene,toluene,xylene, chlorobenzene, orthodichlorobenzene with above-mentioned solvent, usage quantity can be for till the degree of not separating out polymkeric substance.
Polyimide A can prepare by the following method, (1) solution polymerization process, (2) behind the preparation polyamic acid solution, be made into film, and carry out the method for imidization, (3) carry out the method for solid state polymerization after salt such as the half ester salt of HPMDA or imide oligopolymer are made, (4) can adopt known method in the past in addition with the method for tetracarboxylic dianhydride and di-isocyanate reaction.Also can make up these methods is prepared.And the reaction of tetracarboxylic acid composition (Y) and two amine components (Z) also can be carried out in the presence of known in the past catalyzer such as acid, tertiary amine class, acid anhydrides.
In these methods, can directly obtain the organic solvent solution of polyimide A, so the solution polymerization process of preferably following (1)～(3).
(1) will contain two amine components (Z), organic solvent and the mixture of catalysts that contains as required stirs with 10～600rpm and forms homogeneous solution, hold it in 30～90 ℃, add tetracarboxylic acid composition (Y) and as required and the catalyzer that adds.
(2) will contain tetracarboxylic acid composition (Y), organic solvent and the mixture of catalysts that contains as required stirs with 10～600rpm and forms homogeneous solution, hold it in 30～90 ℃, add two amine components (Z) and as required and the catalyzer that adds.
(3) after (1) or (2) method, be warming up to 160～230 ℃, be preferably 180～205 ℃ through 0.1～6 hour.This temperature can be determined according to the boiling point of used organic solvent.After the composition that will discharge outside reaction system captures, temperature was kept 0.5～24 hour, preferably kept 2～12 hours.Afterwards, as required, further add organic solvent, be cooled to proper temperature.
The solution polymerization that is used to prepare polyimide A is also can carry out in the presence of following catalyzer, this catalyzer is preferably and is selected from Trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, trolamine, N, N-dimethylethanolamine, N, at least a in the tertiary amine compounds such as N-diethylethanolamine, triethylenediamine, N-crassitude, N-ethyl pyrrolidine, N-methyl piperidine, N-ethylpiperidine, imidazoles, pyridine, quinoline, isoquinoline 99.9.When using catalyzer, the usage quantity of catalyzer is preferably 0.1～100 mole of % of tetracarboxylic acid composition (Y), more preferably 1～10 mole of %.
Also can add fluorine class, polysiloxane-based etc. tensio-active agent in the organic solvent solution of polyimide A.Thus, can obtain the good tack coat of surface smoothing, polyimide resin film easily.
Kapton is to apply (casting) on the level and smooth support with the sheet glass of release property, metal sheet etc. by the organic solvent solution with above-mentioned polyimide A, and 50～350 ℃ of heating, evaporation is removed organic solvent and made.Be preferably evaporating solvent under the temperature below 120 ℃, form the self-support film after, this film is peeled off from support, fix the end of this film, under the boiling point to 350 of used organic solvent ℃, carry out drying, the preparation polyimide resin film.The pressure of dry environment can be any one of decompression, normal pressure, pressurization.The thickness of polyimide resin film is preferably 1～100 μ m, more preferably 2～50 μ m.Replace the organic solvent solution of polyimide A, polyamic acid solution can be coated on the level and smooth support, 50～350 ℃ of heating, the imidization reaction of dewatering can prepare polyimide resin film thus.
Clad with metal foil lamination body of the present invention comprises insulating substrate, metal level and is configured in the tack coat that is formed by polyimide A between them.
Clad with metal foil lamination body is, the organic solvent solution of polyimide A is coated in insulating substrate and the metal level one or two, organic solvent is removed 50～350 ℃ of evaporations, after forming tack coat, by tack coat that insulating substrate and metal level is superimposed, carry out the method for thermo-compressed then and make; Perhaps, above-mentioned polyimide resin film is configured between insulating substrate and the metal level, carries out the method for thermo-compressed and make.In addition, by on the single face of polyimide resin film, utilize the method for sputtering method, vapour deposition method and electroless plating method etc., directly form metallic film, and on the another side insulating substrate placed and the method for thermo-compressed and after the insulating substrate surface forms tack coat, on the surface of this tack coat, utilize the method for sputtering method, vapour deposition method and electroless plating method etc., directly form the method for metallic film, also can prepare insulating substrate and metal level agglutinating clad with metal foil lamination body securely.
The thickness of tack coat is preferably 1～100 μ m, more preferably 2～50 μ m.The second-order transition temperature of polyimide A is preferably 230～300 ℃ according to selected diamines and difference is generally 200～350 ℃.The temperature of polyimide A more than second-order transition temperature shows cohesiveness, so when second-order transition temperature was too high, the thermo-compressed temperature will be too high, and second-order transition temperature is crossed when low, the thermotolerance deficiency of film self.
Metal level also can be formed by the tinsel that obtains by electrolysis, method such as rolling, also can be as mentioned above directly forms on the surface of the tack coat that forms on the surface of polyimide resin film or the insulating substrate.Metal layer thickness is not particularly limited, and is preferably 1～100 μ m.The material of metal level is preferably copper.In addition, surface treatment is implemented on single face of tinsel (adhesive surface) or two sides, and making surface roughness Rz is 0.1～12 μ m.In general, use when being called the Copper Foil of low crest line (ロ one プ ロ Off ア イ Le), Rz is preferably 0.1～2 μ m, more preferably 0.4～2 μ m, more preferably 1.0～2 μ m.In addition, bonding usefulness not implement the surface-treated tinsel more with the situation that handle with rust-preventive agent etc. on the surface usually, so preferably use after utilizing the wipe surfaces such as cloth of soaking the organic solvent that acetone etc. is arranged.
As long as insulating substrate of the present invention is not particularly limited with the metal level electrical isolation.In addition, insulating substrate comprises soft type and solidly, can use any one.The thickness of insulating substrate is according to mentioned kind and difference is preferably 3～2000 μ m.The soft type insulating substrate can be enumerated, the film of polyimide (except the polyimide A), polybenzimidazole, polybenzoxazole, polymeric amide (comprising arylamine), polyetherimide, polyamidoimide, polyester (comprising liquid crystalline polyester), polysulfones, polyethersulfone, polyetherketone, polyether-ether-ketone etc., be preferably polyimide resin film, specifically can enumerate trade(brand)name " カ プ ト Application EN ", " カ プ ト Application V ", " カ プ ト Application H " (eastern レ デ ユ Port Application (strain) system), trade(brand)name " ア ピ カ Le NPI ", " ア ピ カ Le AH " ((strain) カ ネ カ system) etc.The thickness of this soft type insulating substrate is not particularly limited, and is preferably 3～150 μ m, more preferably 7.5～75 μ m.
The solidly insulating substrate can be enumerated, on the dielectric panel of sheet glass, ceramic plate, plastic plate etc. or metal sheet, form the insulating substrate of insulation film, with thermoplasticity or heat cured various resin impregnation such as liquid crystalline polymers, phenol resins, Resins, epoxy and be blended in molding in the tougheners such as glasscloth, plastic optical fibre cloth or staple glass fibre.The thickness of this solidly insulating substrate is not particularly limited, and is preferably 30～2000 μ m.
Usually can suitably adopt the method for using multistage (vacuum) extrusion machine, use the continuous squeezing method of backer roll etc. etc. as thermal pressure welding method.
The thermo-compressed temperature is preferably 200～400 ℃, and more preferably 250～350 ℃, the second-order transition temperature of used polyimide A is selected above considering.The pressure of thermo-compressed is preferably 0.01～20MPa, more preferably 0.1～10MPa.In addition, in order to remove the gentle bubble that desolvates, preferably under reduced pressure atmosphere, carry out thermo-compressed.
The stripping strength of metal level of utilizing the clad with metal foil lamination body of the present invention that the aftermentioned method measures is as long as for 0.5N/mm is above just practical, be preferably more than the 0.8N/mm.
Embodiment
Describe the present invention in detail below by embodiment.But the present invention is not limited to these embodiment.
The measuring method of physical property is expressed as follows.
(1) IR spectrum
Utilize the JIR-WINSPEC50 of NEC (strain) system to measure.
(2) logarithm viscosities il
The N-N-methyl-2-2-pyrrolidone N-solution of the polyimide of preparation 0.5g/dL.In 30 ℃ of Water Tanks with Temp.-controlled, utilize the liquid level lowering time between the graticule of this solution of Ka Nongfensike viscometer determining, obtain according to following formula.
η=ln (solution lowering time/N-N-methyl-2-2-pyrrolidone N-lowering time)/0.5
Logarithm viscosity, its value is similar to intrinsic viscosity, can easyly obtain.
(3) second-order transition temperature
Obtain by the DSC method.Utilize the DSC-50 of (strain) Shimadzu Seisakusho Ltd. system, measuring the intermediate point second-order transition temperature Tmg that obtains at 40～350 ℃ under with 10 ℃/minute heat-up rate is second-order transition temperature.
(4) water-intake rate of polyimide
Method according to IPC-TM-650 2.6.2.1 is obtained.
With the Kapton of 50.8 * 50.8mm 120 ℃ of dryings after 1 hour, gravimetry (W
0).These thin film dipped in 23 ℃ distilled water 24 hours, behind the moisture of wipe surfaces, rapid test weight (W
1).
Water-intake rate (%)=(W
1-W
0) ÷ W
0* 100
(5) stripping strength of metal level
According to the stripping strength assay method of 90 ° of Copper Foils of peeling off of JIS C 6471, obtain stripping strength (utilizing stripping strength to measure method A) with rotation barrel shape support die.
(6) scolding tin thermotolerance
With reference to JIS C 6471, carry out following test.
Cut out the test film of 10 * 50mm from clad with metal foil lamination body, in humidity 50%, 23 ℃ thermostatic chamber, placed 24 hours.Then, in solder bath (260 ℃ and 280 ℃) floating 20 seconds.Outward appearance such as occurring expanding, peeling off is A when unusual, is C when occurring that outward appearance is unusual.
Embodiment 1
Has the half-moon-shaped agitating wing of stainless steel, nitrogen ingress pipe, the Dean and Stark apparatus (デ イ one Application ス one Network) of band prolong, thermometer, in five mouthfuls of glass round-bottomed flasks of 300 milliliters of glass T-valve, under nitrogen atmosphere, add 2 of 26.00 grams (0.06334 mole), two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP of 2-, refine industry (strain) system of Wakayama), 0.76 the mphenylenediamine (MPD of gram (0.00704 mole), Northeast chemistry (strain) system), 51.04 gamma-butyrolactone (the GBL that restrain as solvent, Mitsubishi Chemical's (strain) system), and as catalyzer 0.356 the gram triethylamine (TEA, Northeast chemistry (strain) system), stir with 100rpm, obtain solution.
In this solution, once add 1 of 15.77 grams (0.07037 mole) respectively, 2,4,5-hexanaphthene tetracarboxylic dianhydride (HPMDA, Mitsubishi's gas chemistry (strain) is made) and the 12.76 N,N-DIMETHYLACETAMIDE (DMAC that restrain, Mitsubishi's gas chemistry (strain) system) after, utilizes the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 5 hours down at 180 ℃.
After adding the DMAC of 96.20 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
After being coated in the polyimide A solution that obtains on the level and smooth sheet glass that is dispersed with the minute quantity releasing agent with coating machine, heating is 1 hour on 100 ℃ hot plate, forms the self-support film.The film of peeling off from sheet glass on the stainless steel molding box with clip fixing several after, in 200 ℃ vacuum drier, placed 5 hours, almost completely remove and desolvate (less than 1 weight %), obtain polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1776,1704 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide A is 1.05dL/g, and second-order transition temperature is 268 ℃, and water-intake rate is 2.1%.
The polyimide A solution that obtains above is coated in the polyimide resin film that thickness is 25 μ m (trade(brand)name: カ プ ト Application 100EN, east レ デ ユ Port Application (strain) system) on, after heating 0.5 hour on 100 ℃ the hot plate, descended dry 5 hours at 200 ℃ in vacuum drier, forming thickness on insulating substrate is the tack coat of 4 μ m.With thickness is that the single face of the electrolytic copper foil (ProductName: 3EC-III, Mitsui Metal Co., Ltd.'s mining industry (strain) system) of 18 μ m carries out roughening treatment on the bonding aspect, and forming Rz is the asperities of 5.0 μ m.Then, by asperities electrolytic copper foil is overlapped on the tack coat.It is clamped with stainless steel mirror board, is inserted between the heat dish of thermocompressor of 330 ℃ of temperature, keep 3 minutes with contact pressure (0MPa) after, under 330 ℃, 5MPa, 5 minutes condition, add thermo-compressed.Then, be inserted between the heat dish of extrusion machine of normal temperature, cool off, obtain clad with metal foil lamination body with 5MPa, 2 minutes condition.
The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 1.09N/mm, and the scolding tin thermotolerance is A.
Embodiment 2
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, add the BAPP of 27.280 grams (0.06645 mole), the m-xylene diamine (MXDA of 0.0914 gram (0.00067 mole), Northeast chemistry (strain) system), the TEA of the NMP of 50.00 grams and 0.34 gram, stir with 100rpm, obtain solution.
In this solution, once add the HPMDA of 15.048 grams (0.06713 mole) and the N-N-methyl-2-2-pyrrolidone N-(NMP of 13.63 grams respectively, Mitsubishi Chemical's (strain) system) after, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 195 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 12 hours at 195 ℃.
After adding the DMAC of 96.37 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1772,1706 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide A is 1.01dL/g, and second-order transition temperature is 262 ℃, and water-intake rate is 1.9%.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.87N/mm, and the scolding tin thermotolerance is A.
Embodiment 3
Except using the polyimide A solution that obtains among the embodiment 2, being the polyimide resin film (trade(brand)name: ア ピ カ Le NPI of 25 μ m as the thickness of insulation layer, (strain) カ ネ カ system) and as the Rz that has of metal level is that the quarry-faced thickness of 6.0 μ m is the electrolytic copper foil (ProductName: JTC of 18 μ m, (strain) day ore deposit マ テ リ ア Le ズ system) outside, other is identical with embodiment 1, obtains clad with metal foil lamination body.
The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.91N/mm, and the scolding tin thermotolerance is A.
Embodiment 4
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, add the HPMDA of 14.573 grams (0.06501 mole), the NMP of 40.00 grams and the TEA of 0.33 gram, stir with 100rpm, obtain solution.
Temporary transient stirring and dissolving behind the MXDA of adding 4.427 grams (0.03250 mole) in this solution, after then once adding the BAPP and 8.51 NMP that restrain of 13.343 grams (0.03250 mole) respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 195 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 6 hours at 195 ℃.
After adding the DMAC of 71.49 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1774,1697 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide A is 0.63dL/g, and second-order transition temperature is 232 ℃, and water-intake rate is 2.2%.Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.95N/mm, and the scolding tin thermotolerance is A.
Embodiment 5
Except using the polyimide A solution that obtains among the embodiment 4, being the rolling aluminium foil (ProductName: 1085 paper tinsels of 90 μ m as the ア ピ カ Le NPI of insulation layer and as metal layer thickness, Japan's foliation (strain) system) outside, other is identical with embodiment 1, obtains clad with metal foil lamination body.
The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 1.08N/mm, and the scolding tin thermotolerance is A.
Embodiment 6
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, add BAPP, the MXDA of 0.923 gram (0.00678 mole), the NMP of 40.00 grams and the TEA of 0.26 gram of 19.266 grams (0.04693 mole), stir, obtain solution with 100rpm.
After in this solution, once adding the HPMDA and 7.82 NMP that restrain of 11.690 grams (0.05215 mole) respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 200 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 5 hours at 200 ℃.
After adding the DMAC of 72.181 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1772,1704 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide A is 0.52dL/g, and second-order transition temperature is 253 ℃, and water-intake rate is 2.2%.
The polyimide A solution that obtains above is coated on the カ プ ト Application 100EN, and after on 100 ℃ the hot plate dry 0.5 hour, 200 ℃ of dryings 5 hours, forming thickness on カ プ ト Application 100EN was the tack coat of 4 μ m in vacuum drier.
Equally, be that the Rz of the electrolytic copper foil (ProductName: FO-WS, Furukawa サ one キ Star ト Off オ イ Le (strain) system) of 9 μ m is that to form thickness on the non-asperities of 1.0 μ m be the tack coat of 4 μ m with thickness.
Then, the カ プ ト Application EN that obtains above and Copper Foil are overlapped between the tack coat mutually backward, identical with embodiment 1, obtain clad with metal foil lamination body.
The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 1.04N/mm, and the scolding tin thermotolerance is A.
Embodiment 7
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, add the BAPP of 27.430 grams (0.06682 mole), the GBL of 50.89 grams and the TEA of 0.34 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the DMAC of 14.979 gram (0.06682 mole) HPMDA and 12.72 grams respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 6 hours at 180 ℃.
After adding the DMAC of 96.39 grams, formed homogeneous solution in 30 minutes,, obtain the polyimide resin solution that solid component concentration is 20 weight % with air cooling to 100 in 10 minutes ℃ at about 130 ℃ of stir abouts.
Except using the polyimide resin solution that obtains above, other is identical with embodiment 1, obtains polyimide resin film.Measure the IR spectrum of this polyimide resin film, its results verification is at ν (C=O) 1774,1706 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide resin is 1.00dL/g, and second-order transition temperature is 263 ℃, and water-intake rate is 1.6%.
Except using the polyimide resin solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.62N/mm, and the scolding tin thermotolerance is A.
Comparative example 1
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, add 4 of 20.624 grams (0.10299 mole), 4 '-diaminodiphenyl oxide (ODA, refine industry (strain) system of Wakayama), the GBL of 52.45 grams and the TEA of 0.52 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the HPMDA and 13.11 DMAC that restrain of 23.088 grams (0.10299 mole) respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 5 hours at 180 ℃.
After adding the DMAC of 94.43 grams, formed homogeneous solution in 30 minutes,, obtain the polyimide resin solution that solid component concentration is 20 weight % with air cooling to 100 in 10 minutes ℃ at about 130 ℃ of stir abouts.
Except using the above-mentioned polyimide resin solution that obtains, other is identical with embodiment 1, obtains polyimide resin film.Measure the IR spectrum of this polyimide resin film, its results verification is at ν (C=O) 1772,1700 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide is 1.06dL/g, and second-order transition temperature is 316 ℃, and water-intake rate is 5.5%.
Except using the polyimide resin solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The metal level of the clad with metal foil lamination body that obtains can be peeled off with the autograph letter list, and its stripping strength is very low.
Comparative example 2
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, the α that adds 19.404 grams (0.05633 mole), α '-two (3-aminophenyl)-1,4-diisopropyl benzene (PVC ス ア ニ リ Application M, Mitsui Chemicals (strain) system), the GBL of 38.44 grams and the TEA of 0.28 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the HPMDA and 9.61 DMAC that restrain of 12.627 grams (0.05633 mole) respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 12 hours at 180 ℃.
After adding the DMAC of 71.96 grams, formed homogeneous solution in 30 minutes,, obtain the polyimide resin solution that solid component concentration is 20 weight % with air cooling to 100 in 10 minutes ℃ at about 130 ℃ of stir abouts.
Except using the polyimide resin solution that obtains above, other is identical with embodiment 1, obtains polyimide resin film.Measure the IR spectrum of this polyimide resin film, its results verification is at ν (C=O) 1774,1704 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide is 0.52dL/g, and second-order transition temperature is 220 ℃, and water-intake rate is 1.5%.
Except using the polyimide resin solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.45N/mm, and the scolding tin thermotolerance is A.
Table 1
| Two amine components | Logarithm viscosities il (dL/g) | Second-order transition temperature (℃) | Water-intake rate (%) | Stripping strength (N/mm) | The scolding tin thermotolerance | |||
| BAPP mole % * | The copolymerization composition | |||||||
| Kind | Mole % | |||||||
| Embodiment 1234567 comparative examples are than 1 to 2 | 90 99 99 50 50 90 100 0 0 | MPD MXDA MXDA MXDA MXDA MXDA - ODA ビスアニリンM | 10 1 1 50 50 13 - 100 100 | 1.05 1.01 1.01 0.63 0.63 0.52 1.00 1.06 0.52 | 268 262 262 232 232 253 263 316 220 | 2.1 1.9 1.9 2.2 2.2 2.2 1.6 5.5 1.5 | 1.09 0.87 0.87 0.95 1.08 1.04 0.62 ＜0.2 0.45 | A A A A A A A - A |
Mole %
*: the ratio of relative HPMDA amount
Embodiment 8
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, 3 of the BAPP of adding 27.244 grams (0.06637 mole), 0.145 gram (0.00067 mole), 3 '-dihydroxyl-4,4 '-benzidine (HAB, refine industry (strain) system of Wakayama), the GBL of 50.90 grams and the TEA of 0.339 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the DMAC of 15.027 gram (0.06704 mole) HPMDA and 12.72 grams respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 5 hours at 180 ℃.
After adding the DMAC of 96.38 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1776,1706 (cm
-1) on have the characteristic absorbance of imide ring.The functional group concentration F of this polyimide A is 0.034meq/g, and the logarithm viscosities il is 1.10dL/g, and second-order transition temperature is 264 ℃, and water-intake rate is 1.9%.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 1.05N/mm, and the scolding tin thermotolerance is A.
Embodiment 9
Except using the polyimide A solution that obtains among the embodiment 8, being the ア ピ カ Le NPI of 25 μ m and being that the quarry-faced thickness of 6.0 μ m is the electrolytic copper foil (ProductName: JTC of 18 μ m as the Rz that has of metal level as the thickness of insulation layer, (strain) day ore deposit マ テ リ ア Le ズ system) outside, other is identical with embodiment 1, obtains clad with metal foil lamination body.
The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 1.10N/mm, and the scolding tin thermotolerance is A.
Embodiment 10
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, 3 of the BAPP of adding 26.956 grams (0.06566 mole), 0.309 gram (0.00203 mole), 5-diamino M-nitro benzoic acid (DBA, the ACROS corporate system), the TEA of the GBL of 50.93 grams and 0.34 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the DMAC of 15.175 gram (0.06769 mole) HPMDA and 12.73 grams respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 4 hours at 180 ℃.
After adding the DMAC of 96.34 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1776,1706 (cm
-1) on have the characteristic absorbance of imide ring.The functional group concentration F of this polyimide A is 0.051meq/g, and the logarithm viscosities il is 0.78dL/g, and second-order transition temperature is 261 ℃, and water-intake rate is 2.0%.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.89N/mm, and the scolding tin thermotolerance is A.
Embodiment 11
Except using the polyimide A solution that obtains among the embodiment 10, being the ア ピ カ Le NPI of 25 μ m and being the rolling aluminium foil (ProductName: 1085 paper tinsels of 90 μ m as metal layer thickness as the thickness of insulation layer, Japan's foliation (strain) system) outside, other is identical with embodiment 1, obtains clad with metal foil lamination body.Rolling aluminium foil is to use after adhesive surface is used the cloth wiping that is impregnated with acetone.
The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.97N/mm, and the scolding tin thermotolerance is A.
Embodiment 12
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, 3 of the BAPP of adding 26.773 grams (0.06522 mole), 0.577 gram (0.00202 mole), 3 '-dicarboxyl-4,4 '-diaminodiphenyl-methane (MBAA, refine industry (strain) system of Wakayama), the GBL of 50.91 grams and the TEA of 0.34 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the DMAC of 15.072 gram (0.06724 mole) HPMDA and 12.73 grams respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 6 hours at 180 ℃.
After adding the DMAC of 96.37 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1776,1706 (cm
-1) on have the characteristic absorbance of imide ring.
The functional group concentration F of this polyimide A is 0.101meq/g, and the logarithm viscosities il is 1.05dL/g, and second-order transition temperature is 263 ℃, and water-intake rate is 1.9%.Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.81N/mm, and the scolding tin thermotolerance is A.
Embodiment 13
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, 4 of the BAPP of adding 26.874 grams (0.06546 mole), 0.430 gram (0.00202 mole), 4 '-diaminobenzophenone (4,4 '-DBP, the ALDRICH corporate system), the GBL of 50.92 grams and the TEA of 0.34 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the DMAC of 15.129 gram (0.06749 mole) HPMDA and 12.73 grams respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 6 hours at 180 ℃.
After adding the DMAC of 96.35 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1776,1704 (cm
-1) on have the characteristic absorbance of imide ring.
The functional group concentration F of this polyimide A is 0.051meq/g, and the logarithm viscosities il is 0.74dL/g, and second-order transition temperature is 262 ℃, and water-intake rate is 1.7%.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.86N/mm, and the scolding tin thermotolerance is A.
Comparative example 3
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, add BAPP, the HAB of 4.005 grams (0.01852 mole), the GBL of 38.43 grams and the TEA of 0.28 gram of 15.436 grams (0.03760 mole), stir, obtain solution with 100rpm.
After in this solution, once adding the DMAC of 12.581 gram (0.05612 mole) HPMDA and 9.61 grams respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 6 hours at 180 ℃.
After adding the DMAC of 71.97 grams, formed homogeneous solution in 30 minutes,, obtain the polyimide solution that solid component concentration is 20 weight % with air cooling to 100 in 10 minutes ℃ at about 130 ℃ of stir abouts.
Except using the polyimide solution that obtains above, other is identical with embodiment 1, obtains Kapton.Measure the IR spectrum of this Kapton, its results verification is at ν (C=O) 1772,1704 (cm
-1) on have the characteristic absorbance of imide ring.The functional group concentration F of this polyimide is 1.235meq/g, and the logarithm viscosities il is 0.89dL/g, and second-order transition temperature is 300 ℃, and water-intake rate is 5.0%.
Except using the polyimide solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 1.00N/mm, and the scolding tin thermotolerance is C.
Table 2
| Two amine components | Functional group concentration F (meq/g) | Logarithm viscosities il (dL/g) | Second-order transition temperature (℃) | Water-intake rate (%) | Stripping strength (N/mm) | The scolding tin thermotolerance | |||
| BAPP mole % | The copolymerization composition | ||||||||
| Kind | Mole % | ||||||||
| Embodiment 89 10 11 12 13 comparative examples are than 3 | 99 99 97 97 97 97 67 | HAB HAB DBA DBA MBAA 4，4’-DBP HAB | 1 1 3 3 3 3 33 | 0.034 0.034 0.051 0.051 0.101 0.051 1.235 | 1.10 1.10 0.78 0.78 1.05 0.74 0.89 | 264 264 261 261 263 262 300 | 1.9 1.9 2.0 2.0 1.9 1.7 5.0 | 1.05 1.10 0.89 0.97 0.81 0.86 1.00 | A A A A A A C |
Embodiment 14
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, add the BAPP of 27.533 grams (0.06707 mole), the GBL of 50.901 grams and the TEA of 0.336 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the HPMDA and 12.725 DMAC that restrain of 14.885 grams (0.06640 mole) respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 3 hours at 180 ℃.
After adding the DMAC of 96.374 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1774,1706 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide A is 0.71dL/g, and second-order transition temperature is 262 ℃, and water-intake rate is 1.7%.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.86N/mm, and the scolding tin thermotolerance is A.
Embodiment 15
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, 4 of the BAPP of adding 14.214 grams (0.03463 mole), 12.757 grams (0.03463 mole), 4 '-two (4-amino-benzene oxygen) biphenyl (BAPB, refine industry (strain) system of Wakayama), the GBL of 50.995 grams and the TEA of 0.350 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the HPMDA and 12.749 DMAC that restrain of 15.524 grams (0.06925 mole) respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 4 hours at 180 ℃.
After adding the DMAC of 96.256 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1779,1704 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide A is 0.95dL/g, and second-order transition temperature is 278 ℃, and water-intake rate is 1.9%.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.81N/mm, and the scolding tin thermotolerance is A.
Embodiment 16
Except using the polyimide A solution that obtains among the embodiment 15, being the ア ピ カ Le NPI of 25 μ m and being that the quarry-faced thickness of 6.0 μ m is the electrolytic copper foil (ProductName: JTC of 18 μ m as the Rz that has of metal level as the thickness of insulation layer, (strain) day ore deposit マ テ リ ア Le ズ system) outside, other is identical with embodiment 1, obtains clad with metal foil lamination body.
The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.85N/mm, and the scolding tin thermotolerance is A.
Embodiment 17
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, add the BAPP of 24.158 grams (0.05885 mole), the p dimethylamine (PXDA of 2.004 grams (0.01471 mole), Mitsubishi's gas chemistry (strain) system), the TEA of the NMP of 50.000 grams and 0.372 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the HPMDA and 13.997 NMP that restrain of 16.490 grams (0.07356 mole) respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 195 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 3 hours at 195 ℃.
After adding the DMAC of 96.023 grams, formed homogeneous solution in 30 minutes at about 130 ℃ of stir abouts, with air cooling to 100 in 10 minutes ℃, obtaining solid component concentration is the polyimide A solution of 20 weight %.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains polyimide A film.Measure the IR spectrum of this polyimide A film, its results verification is at ν (C=O) 1772,1699 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide A is 0.71dL/g, and second-order transition temperature is 261 ℃, and water-intake rate is 2.2%.
Except using the polyimide A solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.85N/mm, and the scolding tin thermotolerance is A.
Embodiment 18
Except using the polyimide A solution that obtains among the embodiment 17, being the ア ピ カ Le NPI of 25 μ m and being the rolling aluminium foil (ProductName: 1085 paper tinsels of 90 μ m as metal layer thickness as the thickness of insulation layer, Japan's foliation (strain) system) outside, other is identical with embodiment 1, obtains clad with metal foil lamination body.Rolling aluminium foil is to use after adhesive surface is used the cloth wiping that is impregnated with acetone.
The stripping strength of the metal level of the clad with metal foil lamination body that obtains is 0.95N/mm, and the scolding tin thermotolerance is A.
Comparative example 4
With embodiment 1 in five mouthfuls of identical glass round-bottomed flasks of using, under nitrogen atmosphere, add 4 of 20.624 grams (0.10299 mole), 4 '-diaminodiphenyl oxide (ODA, refine industry (strain) system of Wakayama), the GBL of 52.45 grams and the TEA of 0.52 gram, stir with 100rpm, obtain solution.
After in this solution, once adding the HPMDA and 13.11 DMAC that restrain of 23.088 grams (0.10299 mole) respectively, utilize the mantle heater heating, utilize about 20 minutes temperature in the reaction system is brought up to till 180 ℃.The distillatory composition is collected, simultaneously temperature in the reaction system was kept 3 hours at 180 ℃.
After adding the DMAC of 94.43 grams, about 130 ℃ of stir abouts formed homogeneous solution in 30 minutes, with air cooling to 100 in 10 minutes ℃, obtained the polyimide resin solution that solid component concentration is 20 weight %.
Except using the polyimide resin solution that obtains above, other is identical with embodiment 1, obtains polyimide resin film.Measure the IR spectrum of this polyimide resin film, its results verification is at ν (C=O) 1772,1700 (cm
-1) on have the characteristic absorbance of imide ring.The logarithm viscosities il of this polyimide is 0.90dL/g, and second-order transition temperature is 315 ℃, and water-intake rate is 5.7%.
Except using the polyimide resin solution that obtains above, other is identical with embodiment 1, obtains clad with metal foil lamination body.The metal level of the clad with metal foil lamination body that obtains can be peeled off with the autograph letter list, and its stripping strength is very low.
Industrial applicibility
Polyimide resin of the present invention has good thermoplastic, solvent soluble and thermotolerance, and water-intake rate is low, cohesiveness is good, so be useful as the bonding layer material of the clad with metal foil lamination body that is used to process printed circuit board, face heating element, electromagnetic shielding material, flat cable etc.
Table 3
| Two amine components | Logarithm viscosities il (dL/g) | Second-order transition temperature (℃) | Water-intake rate (%) | Stripping strength (N/mm) | The scolding tin thermotolerance | ||||
| HPMDA mole % | BAPP mole % | The copolymerization composition | |||||||
| Kind | Mole % | ||||||||
| Embodiment 14 15 16 17 18 comparative examples are than 4 | 99 100 100 100 100 100 | 100 50 50 80 80 - | - BAPB BAPB PXDA PXDA ODA | - 50 50 20 20 100 | 0.71 0.95 0.95 0.71 0.71 0.90 | 262 278 278 261 261 315 | 1.7 1.9 1.9 2.2 2.2 5.7 | 0.86 0.81 0.85 0.85 0.95 ＜0.2 | A A A A A - |
Claims (19)
1. polyimide resin; Wherein, This polyimide resin is by the repetitive of following general formula (1) expression or the polyimide resin that formed by at least a repetitive of the repetitive of described general formula (1) expression and following general formula (2) expression; The ratio of the repetitive of described general formula (1) is total more than 50 % by mole of unit that repeat; Utilizing the METHYLPYRROLIDONE solution of 0.5g/dL is 0.3～2dL/g in the logarithm viscosities il of the described polyimide resin of 30 ℃ of mensuration
In the formula, X is that carbonatoms is that 2～39 aliphatic divalent group, carbonatoms are that 3～39 divalence alicyclic group, carbonatoms are 6～39 divalence aromatic group or by their divalent group that is combined to form, the main chain of X also can have be selected from by-O-,-SO
2-,-CH
2-,-C (CH
3)
2-,-OSi (CH
3)
2-,-C
2H
4O-and-at least a conjugated group in the group that S-formed, X also can have at least a functional group that is selected from the group of being made up of carboxyl, hydroxyl or carbonyl, when having this functional group, the concentration F of functional group is above zero and below the 1meq/g polyimide resin.
2. polyimide resin according to claim 1, wherein, the X in the general formula (2) be between a penylene base or a penylene dimethyl.
3. polyimide resin according to claim 1, wherein, described logarithm viscosities il is 0.3～1dL/g.
4. according to any described polyimide resin in the claim 1 to 3, wherein, the water-intake rate of described polyimide resin is below 2.5%.
5. polyimide resin solution, this polyimide resin solution contains any described polyimide resin and organic solvent in the claim 1 to 4.
6. the preparation method of a polyimide resin is characterized in that, this preparation method comprises and will be selected from by 1,2,4,5-hexanaphthene tetracarboxylic acid, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride and 1,2,4, the operation that at least a tetracarboxylic acid composition (Y) in the group that the reactive derivatives of 5-hexanaphthene tetracarboxylic acid is formed and two amine components (Z) react, described two amine components (Z) are two amine components (Z1) or the mixture that formed by this two amine component (Z1) and two amine components (Z2);
Described polyimide resin is by the repeating unit of following general formula (1) expression or the polyimide resin that formed by at least a repeating unit of the repeating unit of described general formula (1) expression and following general formula (2) expression, and the ratio of the repeating unit of described general formula (1) is for always repeating unitary 50 moles more than the %;
In the formula, X is that carbonatoms is that 2～39 aliphatic divalent group, carbonatoms are that 3～39 divalence alicyclic group, carbonatoms are 6～39 divalence aromatic group or by their divalent group that is combined to form, the main chain of X also can have be selected from by-O-,-SO
2-,-CH
2-,-C (CH
3)
2-,-OSi (CH
3)
2-,-C
2H
4O-and-at least a conjugated group in the group that S-formed, X also can have at least a functional group that is selected from the group of being made up of carboxyl, hydroxyl or carbonyl, when having this functional group, the concentration F of functional group is above zero and below the 1meq/g polyimide resin;
(a) this two amine component (Z1) is for being selected from by 2 at least a compound in the group that two [4-(4-amino-benzene oxygen) phenyl] propane of 2-and reactive derivatives thereof are formed;
(b) this two amine component (Z2) is different with this two amine component (Z1), is to be selected from by NH
2-X-NH
2At least a compound in the group that the diamines of expression and reactive derivatives thereof are formed, this X is same as described above;
When (c) this two amine component (Z) was mixture, the usage quantity of this two amine component (Z1) was that 50 moles of total amount of this two amine component (Z1) and this two amine component (Z2) are more than the %.
7. the preparation method of polyimide resin according to claim 6 is characterized in that, this two amine component (Z1) is for being selected from by 2 at least a compound in the group that two [4-(4-amino-benzene oxygen) phenyl] propane of 2-and reactive derivatives thereof are formed; This two amine component (Z2) is for being selected from least a compound in the group of being made up of mphenylenediamine, m-xylene diamine and their reactive derivatives.
8. the preparation method of polyimide resin according to claim 6, wherein, the logarithm viscosities il of described polyimide resin is 0.3～1dL/g.
9. according to the preparation method of any described polyimide resin in the claim 6 to 8, wherein, describedly be reflected in the organic solvent solution in the presence of catalyzer or not heating and carry out, obtain polyimide resin solution.
10. the preparation method of polyimide resin according to claim 9, wherein, described catalyzer is a tertiary amine.
11. according to the preparation method of claim 9 or 10 described polyimide resins, wherein, described heating is to carry out 2～12 hours under 180 ℃～205 ℃ temperature.
12. the preparation method of a polyimide resin film, wherein, this preparation method comprises the polyimide resin solution that obtains with the described polyimide resin solution of claim 5 or by the described preparation method of claim 9 behind casting on the support, the operation that organic solvent is removed in evaporation.
13. the preparation method of polyimide resin film according to claim 12, wherein, described organic solvent evaporated under the temperature below 120 ℃ removes, form the self-support film after, drying is carried out in the end of fixing this film of peeling off from support under the boiling point to 350 of this organic solvent ℃.
14. clad with metal foil lamination body, wherein, this clad with metal foil lamination body comprises insulating substrate, metal level and is configured in tack coat between described insulating substrate and the metal level by any described polyimide resin in the claim 1 to 3 or by what the polyimide resin that obtains by any described preparation method in the claim 6 to 8 formed.
15. clad with metal foil lamination body according to claim 14, wherein, described tack coat is with the described polyimide resin solution of claim 5 or after being coated on the one or both in insulating substrate and the metal level by the polyimide resin solution that the described preparation method of claim 9 obtains, and organic solvent evaporation is removed form.
16. clad with metal foil lamination body according to claim 14, wherein, described tack coat is to be formed by the polyimide resin film that obtains by the described preparation method of claim 12.
17. according to any described clad with metal foil lamination body in the claim 14 to 16, wherein, the second-order transition temperature of described polyimide resin is below 300 ℃.
18. according to any described clad with metal foil lamination body in the claim 14 to 17, wherein, the surface roughness Rz towards the face of tack coat of described metal level is 0.1～2 μ m.
19., wherein, be more than the 0.5N/mm according to the stripping strength of the metal level of measuring with 90 ° of stripping strength assay methods of peeling off Copper Foil of JIS C6471 according to any described clad with metal foil lamination body in the claim 14 to 18.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005013720 | 2005-01-21 | ||
| JP013720/2005 | 2005-01-21 | ||
| JP020655/2005 | 2005-01-28 | ||
| JP028466/2005 | 2005-02-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101107291A true CN101107291A (en) | 2008-01-16 |
Family
ID=39000558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800027760A Pending CN101107291A (en) | 2005-01-21 | 2006-01-20 | Polyimide resin, polyimide film, and polyimide laminate |
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|---|---|
| CN (1) | CN101107291A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102922809A (en) * | 2012-11-01 | 2013-02-13 | 广东生益科技股份有限公司 | Liquid crystal polymer glass fiber bonding sheet copper-clad plate and preparation method thereof |
| CN103240936A (en) * | 2012-02-10 | 2013-08-14 | 新日铁住金化学株式会社 | Transparent flexible laminate and laminate roll |
| CN104017212A (en) * | 2013-02-28 | 2014-09-03 | 比亚迪股份有限公司 | Polyimide resin, preparation method thereof and polyimide foam |
| CN111405751A (en) * | 2020-04-22 | 2020-07-10 | 上海科谷纳新材料科技有限公司 | Structure for improving performance of MPI (Multi-layer printed Circuit) base material FPC (Flexible printed Circuit) antenna and preparation method |
| CN113795383A (en) * | 2019-05-09 | 2021-12-14 | 三菱瓦斯化学株式会社 | Laminated body |
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2006
- 2006-01-20 CN CNA2006800027760A patent/CN101107291A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103240936A (en) * | 2012-02-10 | 2013-08-14 | 新日铁住金化学株式会社 | Transparent flexible laminate and laminate roll |
| CN103240936B (en) * | 2012-02-10 | 2016-08-24 | 新日铁住金化学株式会社 | Clear flexible duplexer and duplexer volume |
| CN102922809A (en) * | 2012-11-01 | 2013-02-13 | 广东生益科技股份有限公司 | Liquid crystal polymer glass fiber bonding sheet copper-clad plate and preparation method thereof |
| CN102922809B (en) * | 2012-11-01 | 2016-08-10 | 广东生益科技股份有限公司 | A kind of liquid crystal polymer glass fibre bonding sheet, copper-clad plate and preparation method thereof |
| CN104017212A (en) * | 2013-02-28 | 2014-09-03 | 比亚迪股份有限公司 | Polyimide resin, preparation method thereof and polyimide foam |
| CN104017212B (en) * | 2013-02-28 | 2016-12-28 | 比亚迪股份有限公司 | A kind of polyimide resin and preparation method thereof and a kind of polyimide foam |
| CN113795383A (en) * | 2019-05-09 | 2021-12-14 | 三菱瓦斯化学株式会社 | Laminated body |
| CN111405751A (en) * | 2020-04-22 | 2020-07-10 | 上海科谷纳新材料科技有限公司 | Structure for improving performance of MPI (Multi-layer printed Circuit) base material FPC (Flexible printed Circuit) antenna and preparation method |
| CN111405751B (en) * | 2020-04-22 | 2021-04-27 | 上海科谷纳新材料科技有限公司 | Structure for improving performance of MPI (Multi-layer printed Circuit) base material FPC (Flexible printed Circuit) antenna and preparation method |
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