CN104245306B - Flexible metal Clad Laminates - Google Patents
Flexible metal Clad Laminates Download PDFInfo
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- CN104245306B CN104245306B CN201380021222.5A CN201380021222A CN104245306B CN 104245306 B CN104245306 B CN 104245306B CN 201380021222 A CN201380021222 A CN 201380021222A CN 104245306 B CN104245306 B CN 104245306B
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- polyimide
- based resin
- clad laminates
- metal level
- flexible metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
This application provides flexible metal Clad Laminates, wherein metal level is formed on the one or both sides of the insulating barrier being made up of multiple polyimide-based resin layers, and the storage modulus that the polyimide-based resin layer contacted with metal level is at 300 DEG C is 1 × 108Pa or bigger, the storage modulus at 350 DEG C is 1 × 108Pa or less, it is characterised in that product does not crimp little with metalclad bonding strength change in size favorably, after heat treatment, the particularly soldering resistance after moisture absorption are excellent.
Description
Technical field
The present invention relates to the flexible metal Clad Laminates for manufacturing flexible printed circuit board, and special
Levy be product do not crimp and metalclad bonding strength favorably, after heat treatment size become
Change little, and particularly soldering resistance after moisture absorption is excellent.
Background technology
For manufacture the flexible metal Clad Laminates of flexible printed circuit board be conducting metal covering with
The laminate of insulating resin, it can stand fine circuit fabrication and can bend in a narrow space,
Therefore, the trend reduced along with electronic equipment size and weight, its utilization increases day by day.Flexible metal
Clad Laminates is divided into two stratotypes and three stratotypes, compared with two stratotypes, uses three stratotypes of binding agent
It has a problem in that its thermostability and anti-flammability are relatively low, and change in size is big during Technology for Heating Processing.Cause
This, the general trend of currently manufactured flexible printed circuit board is to use two stratotype flexible metal covering laminations
Plate rather than three stratotypes.
Decline according to current thinness trend and the weight of circuit, length and size, double-sided metal bag
The use of laminate increases day by day.Double sided metal clad laminate typically by laminated metal foil and
The TPI formed on insulating barrier outermost layer manufactures, but it has a problem in that owing to there is heat
Plastic polyimide resin, after insulating barrier moisture absorption, soldering resistance is deteriorated.Particularly, weld normally
Temperature is in the level of 200 DEG C, but is 250 owing to becoming universal and its temperature without Pb welding procedure
DEG C or higher, the soldering resistance after moisture absorption just becomes more and more important.
Patent documentation 1 has illustrated following situation as known technology: uses and has special construction
Polyimide resin is as thermoplastic polyimide resin layer, and in the case, moisture absorption heat resisting temperature is only
Being only 260 DEG C, therefore, under 300 DEG C or higher critical conditions, soldering resistance will exist asks
Topic.
Summary of the invention
Technical problem
It is an object of the present invention to provide the flexible metal covering lamination for manufacturing printed circuit board (PCB)
Plate and manufacture method thereof, and have by providing flexible metal Clad Laminates to solve association area
In the purpose of problem, wherein said flexible metal Clad Laminates is under 300 DEG C or higher temperature
After moisture absorption, soldering resistance is good, product does not crimp high and thermally treated with the bonding strength of Copper Foil
After change in size little.
Issue-resolution
In a total aspect, it is provided that flexible metal Clad Laminates, wherein metal level is formed at
On the one or both sides of the insulating barrier being made up of multiple polyimide-based resin layers, and contact with metal level
Polyimide-based resin layer storage modulus at 300 DEG C be 1 × 108Pa or bigger, at 350 DEG C
Under storage modulus be 1 × 108Pa or less.
The advantageous effects of invention
The invention provides flexible metal Clad Laminates, wherein the soldering resistance after moisture absorption is good, produce
It is little that product do not crimp high and after heat treatment the change in size of the bonding strength with Copper Foil.
Detailed description of the invention
Hereinafter, the invention provides flexible metal Clad Laminates, wherein metal level be formed at by
On the one or both sides of the insulating barrier that multiple polyimide-based resin layers are constituted, and contact with metal level
Polyimide-based resin layer storage modulus at 300 DEG C is 1 × 108Pa or bigger, at 350 DEG C
Storage modulus be 1 × 108Pa or less.
Providing flexible metal Clad Laminates, plurality of polyimide-based resin layer has such
Form, the most thermoplastic polyimide-based resin bed, Thermocurable polyimide base resin bed and thermoplasticity
Polyimide-based resin layer stratification successively.
Additionally, the polyimide-based resin layer contacted with metal level is glass transition temperature is 300 DEG C
Or lower thermoplastic polyimide-based resin bed.
The polyimide-based resin layer contacted with metal level is setting-out line between 100 DEG C to 200 DEG C
Thermal coefficient of expansion is 50ppm/K or less.
Additionally, according to the present invention, at the flexible metal covering lamination manufactured by polyimide-based resin layer
In plate, after processing 72 hours under conditions of 40 DEG C and 90% relative humidity, moisture absorption proper alignment temperature
It is 300 DEG C or higher, and is 1.0kgf/cm or bigger with the bonding strength of metal level.
Additionally, the invention provides flexible metal Clad Laminates, the polyamides wherein contacted with metal level
Imido grpup resin bed comprise 50 to 100 moles of % by the construction unit represented by formula 1 below.
[chemical formula 1]
-the X-comprised in chemical formula 1 is to comprise one or two or more the virtues selected from having structure
Fragrant race diamino compounds, and can be used alone or be used by copolymerization.
-X1-selected from-O-,-CO-,-S-,-SO2-、-C(CH3)2-、-CONH-、-C(CF3)2-、
-(CH2)-or a combination thereof.
[chemical formula 1] comprisesFor comprising one or two or more selected from having structure
Dianhydride, and can be used alone or be used by copolymerization.
Hereinafter, will mainly the structure of the present invention be described in detail.
The invention provides the flexible metal Clad Laminates with multiple structure, wherein clad shape
Become on the one or both sides of insulating barrier, and described insulating barrier is by multiple polyimide-based resin structures
Become.
Multiple polyimide-based resin layers have such form, the most thermoplastic polyimide-based resin
Layer, Thermocurable polyimide base resin bed and thermoplastic polyimide-based resin bed stratification successively.
Flexible metal Clad Laminates can be by forming single polyimide-based tree on clad layer
Lipid layer manufactures, but in the case, there is problems with.First, be used alone thermosetting gather
In the case of amide based resins layer, low with the bonding strength of metal forming, owing to there is not thermoplasticity polyamides
Amine resin layer and cannot be carried out manufacture the metalclad hot lamination process of double-faced flexible, and exist erosion
The problem that before and after quarter, product all occurs curling.By contrast, it is being used alone thermoplasticity polyamides
In the case of imido grpup resin bed, owing to the thermal linear expansion coefficient of insulating barrier is high, after heat treatment
Change in size is big, and exists before etching and product all occurs curling afterwards problem.Therefore, structure
The insulating barrier becoming the flexible metal Clad Laminates of the present invention has by multiple polyimide-based resin layers
The multiple structure constituted, and by thermoplastic polyimide-based resin bed, Thermocurable polyimide Ji Shu
Lipid layer and thermoplastic polyimide-based resin bed are constituted.
According to the present invention, thermoplastic polyimide-based resin bed means the polyimides contacted with metal level
Base resin bed, it is characterised in that the storage modulus at 300 DEG C is 1 × 108Pa or bigger, at 350 DEG C
Under storage modulus be 1 × 108Pa or less.
Specifically, it is preferable that the storage modulus at 300 DEG C is 1 × 108Pa or bigger and
1×1010Pa or less, the storage modulus at 350 DEG C is 1 × 108Pa or less and 1 × 105Pa
Or it is bigger.
Storage modulus at 300 DEG C is less than 1 × 108Soldering resistance in the case of Pa, after moisture absorption
Aspect has problems；And in storage modulus more than 1 × 1010In the case of Pa, problematically, material
Fragility increase, and bending property reduce.Additionally, the storage modulus at 350 DEG C is more than 1 × 108Pa
In the case of, thermoplasticity is not enough；And in storage modulus less than 1 × 105In the case of Pa, due to resin
Fusing flowing and exist be difficult to hot lamination process problem.
Additionally, the glass transition temperature of the thermoplastic polyimide-based resin bed of the present invention can be
300 DEG C or lower.It is highly preferred that glass transition temperature is 200 DEG C to 300 DEG C.
In the case of thermoplastic polyimide-based resin bed is unsatisfactory for aforementioned condition, such as, if glass
Glass transition temperature is higher than 300 DEG C, and the storage modulus measured at 350 DEG C is more than 1 × 108Pa,
Then the soldering resistance after moisture absorption is favourable, but the illiquidity of at high temperature resin, therefore exist
Hot lamination process and strong with the bonding of another substrate (such as, cover layer and preimpregnation material) can not be carried out
Spend low problem.In view of the problems referred to above, constitute the thermoplastic polyimide-based resin bed of the present invention
Glass transition temperature is 300 DEG C or lower, and the storage modulus at 350 DEG C is 1 × 108Pa
Or it is less.
If be immersed in by the polyimide resin after moisture absorption in high-temperature solder bath, then the moisture absorbed is fast
Speed volatilization, may occur in which following defect: such as between polyimide resin layer or polyimide resin layer
Separate with the interface layer between clad layer, resin bed bubbles and expands.If polyamides is sub-
Polyimide resin is immersed in high-temperature solder bath, then the moisture absorbed in resin bed evaporates rapidly, now thinks
Only when the storage modulus of polyimide resin is in the level that the water vapor pressure of moisture can be sustained, no
The open defect by being immersed in solder bath can be formed.Studied based on this viewpoint, drawn
It is concluded that at 300 DEG C measure storage modulus should be 1 × 108Pa or bigger, it is therefore an objective to even if
Under conditions of 40 DEG C and 90% relative humidity moisture absorption 72 hours or the most still have 300 DEG C or
Higher moisture absorption soldering resistance, by so, can manufacture and have soldering resistance after moisture absorption excellent especially
Flexible metal Clad Laminates.
Additionally, the thermoplastic polyimide-based resin bed contacted with metal level 100 DEG C to 200 DEG C it
Between setting-out line linear thermal expansion coefficient be 50ppm/K or less.
More specifically, it is preferable to ground, thermal linear expansion coefficient is 17ppm/K to 50ppm/K.
The thermal linear expansion coefficient of whole insulating barrier should be low to prevent flexible metal Clad Laminates
Curling and improve dimensional stability after heat treatment.Due to thermoplastic polyimide-based resin bed extremely
The thermal linear expansion coefficient of Thermocurable polyimide base resin bed is high, it is necessary to control thermoplasticity polyamides sub-
The thermal linear expansion coefficient of amine resin layer is to control the thermal linear expansion coefficient of whole insulating barrier.Need
There is the thermoplastic polyimide-based resin bed of high storage modulus at elevated temperatures to control thermoplastic
The thermal linear expansion coefficient of property polyimide-based resin layer.The thermoplastic polyimide-based resin of the present invention
The storage modulus that layer measures at 300 DEG C is 1 × 108Pa or bigger, due to storage modulus at high temperature
It is high, thus setting-out line linear thermal expansion coefficient is 50ppm/K or more at 100 DEG C to 200 DEG C
Little.
Then, the polyimide-based resin according to the present invention will be described.
The precursor of the polyimide-based resin used in the present invention is having by making diamidogen and acid dianhydride
In machine solvent, reaction obtains.In inert atmosphere (such as argon or nitrogen), diamidogen is with slurry form
Dissolve or diffusion in organic solvent, add acid dianhydride, its be solid-state or with slurry form dissolving or
Diffusion is in organic solvent.
The solvent used during synthesis of polyimides precursor solution is not particularly limited, as long as before polyimides
Body dissolves.The example can include solvent based on sulfoxide, and such as dimethyl sulfoxide and diethyl are sub-
Sulfone)；Solvent based on Methanamide, such as DMF and N, N-diethylformamide；
Solvent based on acetamide, such as N,N-dimethylacetamide and N, N-diethyl acetamide；Based on
The solvent of ketopyrrolidine, such as METHYLPYRROLIDONE and NVP；Based on
The solvent of phenol, such as phenol, orthoresol, metacresol or paracresol, xylenol, halogenated phenol and youngster
Tea phenol；Solvent based on ether, such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether., tetraethylene glycol dimethyl ether,
Oxolane and bibasie amino acid (dioxy acid)；Solvent based on alcohol, such as methanol, ethanol and fourth
Alcohol；Cellosolve, such as butyl cellosolve；Hexamethyl phosphoramide and gamma-butyrolacton etc., these examples are preferred
Use alone or as mixture, additionally, aromatic hydrocarbon, such as dimethylbenzene and toluene can be used.
According to the present invention, the dianhydride comprised in multiple polyimide-based resin layers is not particularly limited, only
Wanting dianhydride is acid type dianhydride, and the example can include aliphatic or Alicyclic tetracarboxylic acid dianhydride, example
As 2,2 ' hexafluoro propylidene two butanoic acid dianhydrides, 2, double (4-hydroxyphenyl) propane dibenzoate-3 of 2-, 3 ' 4,4 '
Tetracarboxylic dianhydride, butane tetracarboxylic acid dianhydride, 1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides, 1,3-dimethyl
-1,2,3,4-Tetramethylene. tetrabasic carboxylic acids, 1,2,3,4-Pentamethylene. tetracarboxylic dianhydrides, 2,3,5-tricarboxylic cyclopentyl second
Acid dianhydride, 3,5,6-tri-carboxyl norphonane-2-acetic acid dianhydrides, 2,3,4,5-oxolane tetrabasic carboxylic acids two
Acid anhydride, 5-(2,5-bis-epoxide tetrahydrofuran base)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride and bicyclo-
[2,2,2]-octyl-7-ketone-2,3,5,6-tetracarboxylic dianhydrides；With aromatic tetracarboxylic acid's dianhydride such as Pyromellitic Acid
Dianhydride, 3,3 ' 4,4 ' benzophenone tetracarboxylic dianhydride, 3,3 ' 4,4 ' xenyl sulfone tetracarboxylic dianhydrides, Isosorbide-5-Nitrae, 5,8-
Naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydrides, 3,3 ' 4,4 ' xenyl ether tetracarboxylic dianhydrides,
3,3 ' 4,4 ' dimethyl diphenyl silane tetracarboxylic dianhydrides, 3,3 ' 4,4 ' tetraphenyl silane tetracarboxylic dianhydrides,
1,2,3,4-furan tetracarboxylic dianhydride, 4,4 ' double (3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '
Double (3,4-di carboxyl phenyloxy) sulfobenzide. dianhydride, 4,4 '-bisphenol A dianhydride, 3,3 ' 4,4 ' the different Asias of perfluor
Propyl group O-phthalic acid dianhydride, 3,3 ' 4,4 '-biphenyl tetracarboxylic dianhydride, double (phthalic acid) phenyl oxygen
Change phosphine dianhydride, to phenylene-bis-(triphenyl phthalic acid) dianhydride, metaphenylene-bis-, (triphenyl is adjacent
Phthalic acid) dianhydride, double (triphenyl phthalic acid)-4,4 ' diphenyl ether dianhydride, 3,3 ', 4,4 '-hexichol
Ketone tetracarboxylic dianhydride and double (triphenyl phthalic acid)-4,4 ' diphenyl methane dianhydride.
According to the present invention, the diamidogen comprised in multiple polyimide-based resin layers is not subject to
Limiting, the example can include aromatic diamine, such as P-pHENYLENE dI AMINE, m-phenylenediamine, 4,4 '
Diaminodiphenyl-methane, 4,4 ' diamino-diphenyl ethane, 4,4 ' diamino-diphenyl ethers, 4,4 ' two
Aminophenyl-thioether, 4,4 ' diamino-phenyl sulfones, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4 ' diaminourea
Xenyl, 3,5-diaminourea-benzoic acid, 5-amino-1-(4 ' aminophenyl)-1,3,3-trimethyl indane, 6-
Amino-1-(4 ' aminophenyl)-1,3,3-trimethyl indane, 4,4 ' diaminobenzene formailides, 3,5-diamino
Base-3 ' trifluoromethylbenzoyl aniline, 3,5-diaminourea-4 ' trifluoromethylbenzoyl aniline, 3,4 ' diaminos
Base diphenyl ether, 2,7 diamin of luorene, 2,2-double (4-aminophenyl) HFC-236fa, 4,4 ' methylene-bis-
(2-chloroaniline), 2,2 ' 5,5 ' four chloro-4,4 '-benzidine base, 2,2 ' two chloro-4,4 ' diaminourea-5,5 ' two
Methoxyl biphenyl base, 3,3 ' dimethoxy-4 's, 4 ' diamino-phenyls, 4,4 diaminourea-2,2 ' double (fluoroforms
Base) xenyl, 2, double [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, the double [4-(4-amino-benzene oxygen) of 2-
Phenyl] HFC-236fa, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4, double (4-the amino-benzene oxygen)-xenyl of 4-,
1,3-double (4-amino-benzene oxygen) benzene, 9,9-double (4-aminophenyl) fluorenes, 4,4 ' (to phenylene isopropylidenes)
Diphenylamines, 4,4 ' (metaphenylene isopropylidene) diphenylamines, 4,4 '-oxygen diphenylamines, 2,2 ' double [4-(4-amino
-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa and 4,4 ' double [4-(4-amino-2-trifluoromethyl) benzene oxygen
Base]-octafluoro phenyl；Aromatic diamine, such as diaminourea 4-phenyl-thiophene, it has and is bonded to fragrance
Hetero atom in addition to nitrogen-atoms on two amino of ring and corresponding amino；Aliphatic diamine and fat
Ring race diamidogen, such as 1,1-m-xylene diamine, 1,3-propane diamine, tetra-methylenedimine, five methylenes
Base diamidogen, eight methylene diamine, nine methylene diamine, 4,4-diaminoheptane methylene diamine, Isosorbide-5-Nitrae-
Diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclo-penta diethylenediamine, hexahydro-4,7-bridge is sub-
Methyl Asia indanyl dimethylene diamidogen and 4,4 ' di-2-ethylhexylphosphine oxides (cyclohexylamine) etc..
Specifically, it is contemplated that above-mentioned physical property, the thermoplastic polyimide-based resin of the present invention is constituted
What layer comprised 50 to 100 moles of % is suitable by the construction unit represented by following [chemical formula 1].
[chemical formula 1]
-the X-comprised in chemical formula 1 is to comprise one or two or more the virtues selected from having structure
Fragrant race diamino compounds, and can be used alone or be used by copolymerization.
-X1-selected from-O-,-CO-,-S-,-SO2-、-C(CH3)2-、-CONH-、-C(CF3)2-、
-(CH2)-or a combination thereof.
[chemical formula 1] comprisesFor comprising one or two or more selected from having structure
Dianhydride, and can be used alone or be used by copolymerization.
More specifically, the invention provides flexible metal Clad Laminates, wherein-X1-for comprising-O-
Aromatic series diamino compounds,For comprising one or two or more selected from having structure
Dianhydride.
Suitably, the thermoplastic polyimide-based resin bed of the present invention comprises 50 to 100 moles of %
By the construction unit represented by following [chemical formula 1].In the case of content is less than 50 moles of %,
Storage modulus at 350 DEG C is more than 1 × 108Pa, and thermoplastic polyimide resin layer is at high temperature
Illiquidity, therefore exist can not carry out hot lamination process problem.
The polyimide-based resin mentioned in the present invention include all have imide ring (as following [change
Formula 2]) resin, the example can include polyimides, polyamidoimide, polyesterimide and
Siloxanes degeneration polyimides etc..Additionally, in addition to the one matter of polyimide-based resin, also
Including the mixture shape being wherein mutually mixed by aforementioned polyimide-based resin and other fluoropolymer resin
The material become.Additionally, also include being prone to be coated the polyamides Asia that the additive of technique mixes with other
Amine resin, described additive such as curing accelerator (such as pyridine and quinoline), coupling agent (example
Such as silane), cohesive supply agent (adhesiveness provider) (such as epoxy resin), froth breaking
Agent and levelling agent.
[chemical formula 2]
The method of the flexible metal Clad Laminates manufacturing the present invention includes the tape casting and laminating.
Flexible metal Clad Laminates is manufactured as follows: by polyamide acidic group resin (polyamides by the tape casting
The precursor of imido grpup resin) apply on the metal layer, and formed poly-by heat or chemosetting technique
Imide resin bed.Additionally, the tape casting also includes by metal level is soft with one side by the tape casting
Property double sided metal clad laminate manufactured by Metallic Clad Laminates heat lamination.
Flexible metal Clad Laminates is manufactured as follows: previously fabricated have thermoplasticity polyamides by laminating
Imido grpup resin bed, Thermocurable polyimide base resin bed and thermoplastic polyimide-based resin bed are many
The polyimide base film of Rotating fields, and on its one or both sides heat lamination metal level to manufacture.
In this article, thermoplastic polyimide resin layer comprises [being changed by following of 50 to 100 moles of %
Formula 1] represented by construction unit, such as, can make the pyromellitic acid anhydride as acid dianhydride and
As the 1 of diamidogen, 3-double (4-amino-benzene oxygen) benzene reaction is so that its content is based on generating amic acid
All polyimides is calculated as 50 to 100 moles of %, can apply amic acid and to its heating to carry out Asia
Amination, thus manufactures thermoplastic polyimide resin layer.
Thermoset polyimide resin layer is the most unrestricted, but according to the reality of the present invention
Example, can make the P-pHENYLENE dI AMINE as diamidogen and 4,4 '-oxygen diphenylamines with as acidity dianhydride
3,3 ', 4, the reaction of 4 '-biphenyl tetracarboxylic dianhydride is so that its content is based on generating the whole poly-of amic acid
Acid imide is calculated as 50 to 100 moles of %, can apply amic acid and to its heating to carry out imidization,
Thus manufacture thermoset polyimide resin layer.
In the case, imidization is carried out by dehydration condensation, it is preferable that reaction temperature is
100 DEG C to 400 DEG C, the required response time is 10 minutes to 24 hours, and it is the most not
It is confined to this.
The solvent used in synthesis is the most unrestricted, as long as polyimide precursor
Polyamic acid dissolves, and can use solvent based on sulfoxide, and such as dimethyl sulfoxide and diethyl are sub-
Sulfone；Solvent based on Methanamide, such as DMF and N, N-diethylformamide；
Solvent based on acetamide, such as N,N-dimethylacetamide and N, N-diethyl acetamide；Based on
The solvent of ketopyrrolidine, such as METHYLPYRROLIDONE and NVP；Based on
The solvent of phenol, such as phenol, orthoresol, paracresol or metacresol, xylenol, halogenated phenol and youngster
Tea phenol；Solvent based on ether, such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether., tetraethylene glycol dimethyl ether,
Oxolane and dihydroxy acid；Solvent based on alcohol, such as methanol, ethanol and butanol；Cellosolve, example
Such as butyl cellosolve；Hexamethyl phosphoramide and gamma-butyrolacton etc., it is preferably alone or as mixing
Thing uses, and additionally, even it be also possible to use aromatic hydrocarbon, such as dimethylbenzene and toluene.
The metal level constituting flexible metal Clad Laminates means conducting metal, as copper, aluminum, silver, palladium,
Nickel, chromium, molybdenum and tungsten, and include its alloy or mixture.It is said that in general, copper is widely used, but golden
Genus is not limited thereto.Additionally, the metal level of the present invention also including, the surface of wherein metal level is stood
Physically or chemically surface processes to increase the material of the bonding strength between clad and resin bed.
The example of the painting method that can be applicable to the present invention includes blade coating, roller coat, die coating and curtain coating etc.,
Described method is unrestricted, as long as described method meets the purpose that the present invention is pursued.Can use
The semi-solid preparation solidified in advance or the polyimide solution and the polyimide precursor that are fully cured state are molten
Liquid is as coating solution.
It is optionally used after application and is dried and the technique of solidification insulating barrier, can use multiple known
Method, such as hot blast solidification method, IR solidification method, batch-type solidification method, continuous way solidification method and
Chemical curing method.
Hereinafter, will the present invention is described in detail by EXPERIMENTAL EXAMPLE.But, the present invention is also
It is not limited to these embodiments.
The abbreviation used in embodiment is as follows.
DMAc:N, N-dimethyl acetylamide
Double (4-amino-benzene oxygen) benzene of TPE-R:1,3-
P-PDA: P-pHENYLENE dI AMINE
ODA:4,4 '-oxygen diphenylamines
Double (4-amino-benzene oxygen) phenyl-propane of BAPP:2,2-
DABA:3,5-diaminourea-benzoic acid
BPDA:3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride
PMDA: pyromellitic acid anhydride
BPADA:4,4 '-bisphenol A dianhydride
BTDA:3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride
TMEG: ethylene glycol bis (trimellitic anhydride)
The physical property mentioned in the present invention is measured according to following method.
● thermal linear expansion coefficient
Under the tension force of blanket of nitrogen and 0.03N, Mettler-Toledo GmbH is used to manufacture
TMA/SDTA 861e, is being warming up to 400 DEG C same by temperature from 30 DEG C with the speed of 5 DEG C/min
Time measure thermal linear expansion coefficient.With 25 DEG C in 100 DEG C to 200 DEG C intervals in the numerical value that will measure
For the meansigma methods of unit setting-out line linear thermal expansion coefficient be set as between 100 DEG C to 200 DEG C linear
Thermal coefficient of expansion.
● storage modulus
In blanket of nitrogen, under conditions of the displacement of the tension force of 0.1N, the frequency of 10Hz and 30 μm,
Use the DMA/SDTA 861e that Mettler-Toledo GmbH manufactures, with the speed of 5 DEG C/min
Rate by temperature from 30 DEG C be warming up to 400 DEG C while measure storage modulus.
● glass transition temperature
Under conditions of identical with measuring storage modulus, use DMA, now, the Tan δ that will obtain
Maximum be considered as glass transition temperature.
● the evaluation of TPI
As for the thermoplastic polyimide-based resin mentioned in the present invention, by the storage modulus at 350 DEG C
It is 1 × 108The polyimide-based resin of Pa or less is considered as thermoplastic polyimide-based resin, and will
Storage modulus at 350 DEG C is 1 × 108The situation of Pa or bigger is considered as Thermocurable polyimide Ji Shu
Fat.Storage modulus is measured based on said method.
● moisture absorption soldering resistance
On the Constant Temperature and Humidity Chambers of 40 DEG C/90% relative humidity, the sample of 5cm × 5cm size is entered
Row pretreatment 72 hours or more long, and sample is dipped in the solder bath of 300 DEG C.Outside not resulting in
The situation seeing defect (such as expand and separate with layer) is set to pass through, and the situation causing open defect is set
For failure.In the case of one side copper clad laminate, the sample with Copper Foil and insulating barrier is commented
Valency, it is not necessary to remove Copper Foil.In the case of double-sided copper-clad laminate, remove the laggard of Copper Foil in one side
Row is evaluated, and evaluates each face respectively.
● with the bonding strength of Copper Foil
It is measured based on JIS-C6471.
[synthetic example 1]
At normal temperatures, p-PDA and ODA of 90: 10 moles of % ratios is being dissolved completely in
After in DMAc, in solution, gradually add the BPDA of 100.9 moles of %.Make mixture in room temperature
Lower reaction 24 hours.In the case, the solids content in whole solution is set as 13 weight %.
[synthetic example 2 to 5]
Under the preparation condition identical with synthetic example 1, according to the component described in [table 1] and
Content is prepared.
Table 1
[table 1]
* the E ' at 300 DEG C: the storage heat at 300 DEG C
* the E ' at 350 DEG C: the storage heat at 350 DEG C
* CTE: setting-out line linear thermal expansion coefficient in the range of 100 DEG C to 200 DEG C
* Tg: glass transition temperature
[embodiment 1]
The polyamic acid solution prepared by [synthetic example 2] is applied to the cathode copper of 12 μ m-thick
On paper tinsel (the F2WS Copper Foil being made up of Furukawa circuit paper tinsel, roughness Rz=2.0 μm), so
After at 140 DEG C, be dried to form the first polyimide precursor layer.Will be by [synthetic example
1] polyamic acid solution prepared is applied on a face of the first polyimide precursor layer, then exists
The second polyimide precursor layer it is dried to form at 140 DEG C.Afterwards, will be by [synthetic example
2] polyamic acid solution prepared is applied on a face of the second polyimide precursor layer, then exists
The 3rd polyimide precursor layer it is dried to form at 140 DEG C.Under nitrogen atmosphere, the layer that will manufacture
Pressing plate is heated to 385 DEG C from 150 DEG C, carries out 9 minutes.After hardening, the first polyimide precursor
In layer, the second polyimide precursor layer and the 3rd polyimide precursor layer, each thickness respectively reaches
2.5 μm, 14 μm and 3 μm.Being evaluated the performance of laminate, result is described in [table 2].
[embodiment 2]
By method same as in Example 1, manufacture flexible metal according to the Rotating fields in [table 2]
Clad Laminates.
[comparative example 1 to 3]
By method same as in Example 1, manufacture flexible metal according to the Rotating fields in [table 2]
Clad Laminates.
[table 2]
[table 2]
Claims (6)
1. a flexible metal Clad Laminates, wherein metal level is formed at by thermoplastic polyimide-based
Resin bed/Thermocurable polyimide base resin bed/thermoplastic polyimide-based resin bed stratification successively is constituted
Insulating barrier one or both sides on, the described polyimide-based resin layer contacted with described metal level exists
Storage modulus at 300 DEG C is more than 1 × 108Pa, the storage modulus at 350 DEG C is 1 × 108Pa or more
Little, and process after 72 hours under conditions of 40 DEG C and 90% relative humidity, moisture absorption proper alignment temperature
Degree is 300 DEG C or higher, is 1.0kgf/cm or bigger with the bonding strength of described metal level.
2. the flexible metal Clad Laminates described in claim 1, wherein contacts with described metal level
Described polyimide-based resin layer storage modulus at 300 DEG C is: 1 × 108Storage at Pa ＜ 300 DEG C
Can modulus≤1 × 1010Pa, the storage modulus at 350 DEG C is: 1 × 105Energy storage mould at Pa≤350 DEG C
Amount≤1 × 108Pa。
3. the flexible metal Clad Laminates described in claim 1, wherein contacts with described metal level
Described polyimide-based resin layer be glass transition temperature be that the thermoplasticity polyamides of 300 DEG C or lower is sub-
Amine resin layer.
4. the flexible metal Clad Laminates described in claim 1, wherein contacts with described metal level
Described polyimide-based resin layer setting-out line linear thermal expansion coefficient between 100 DEG C to 200 DEG C is
50ppm/K or less.
5. the flexible metal Clad Laminates according to any one of Claims 1-4, wherein with described
Metal level contact described polyimide-based resin layer comprise 50 moles of % to 100 mole of % by with
Construction unit represented by lower chemical formula 1:
[chemical formula 1]
-the X-comprised in chemical formula 1 is to comprise one or two or more the aromatic series selected from having structure
Diamino compounds, and can be used alone or used by copolymerization；
-X1-selected from-O-,-CO-,-S-,-SO2-、-C(CH3)2-、-CONH-、-C(CF3)2-、-(CH2)-
Or a combination thereof, and
Chemical formula 1 comprisesFor comprising one or two or more the dianhydrides selected from having structure,
And can be used alone or used by copolymerization:
6. the flexible metal Clad Laminates described in claim 5, wherein-X-is the virtue comprising having structure
Fragrant race diamino compounds:
-X1-be-O-, andFor comprising one or two or more the dianhydrides selected from having structure:
Applications Claiming Priority (3)
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|---|---|---|---|
| KR10-2012-0042577 | 2012-04-24 | ||
| KR1020120042577A KR101416782B1 (en) | 2012-04-24 | 2012-04-24 | Flexilbe Metal Clad Laminate |
| PCT/KR2013/003423 WO2013162238A1 (en) | 2012-04-24 | 2013-04-23 | Flexible metal clad laminate |
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| CN104245306B true CN104245306B (en) | 2016-11-16 |
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| JP (1) | JP6258921B2 (en) |
| KR (1) | KR101416782B1 (en) |
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| KR101720218B1 (en) * | 2015-01-29 | 2017-03-27 | 에스케이이노베이션 주식회사 | Low hygroscopicity flexible metal clad laminate |
| JP6908590B2 (en) * | 2016-03-17 | 2021-07-28 | 日鉄ケミカル＆マテリアル株式会社 | Polyamic acid, thermoplastic polyimide, resin film, metal-clad laminate and circuit board |
| KR102268762B1 (en) * | 2016-06-03 | 2021-06-25 | 가부시키가이샤 아리사와 세이사쿠쇼 | Manufacturing method of flexible metal clad laminate |
| CN108181342B (en) * | 2017-12-11 | 2021-06-25 | 广州兴森快捷电路科技有限公司 | Flexible plate detection method |
| KR102491338B1 (en) * | 2018-01-26 | 2023-01-27 | 주식회사 넥스플렉스 | flexible metal clad laminate and THERMOPLASTIC POLYIMIDE PRECORSOR COMPOSITION for flexible metal clad laminate |
| KR102548414B1 (en) * | 2018-03-13 | 2023-06-29 | 주식회사 넥스플렉스 | flexible metal clad laminate |
| JP7122162B2 (en) * | 2018-06-01 | 2022-08-19 | 株式会社カネカ | Thermoplastic Polyimide Films, Multilayer Polyimide Films, and Flexible Metal-Clad Laminates |
| JP7212515B2 (en) | 2018-12-26 | 2023-01-25 | 日鉄ケミカル＆マテリアル株式会社 | Metal-clad laminates and circuit boards |
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| JP3986949B2 (en) * | 2002-11-20 | 2007-10-03 | 株式会社巴川製紙所 | Flexible metal laminate for flexible printed circuit board |
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| CN101065242A (en) * | 2004-12-03 | 2007-10-31 | 三井化学株式会社 | Polyimide metal laminate and suspension for hard disk using same |
| CN101096452A (en) * | 2006-06-26 | 2008-01-02 | 财团法人工业技术研究院 | Method for making thermoplastic polyimide combination and two-side soft copper foil substrate |
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| KR20130119631A (en) | 2013-11-01 |
| TWI603839B (en) | 2017-11-01 |
| JP2015515402A (en) | 2015-05-28 |
| CN104245306A (en) | 2014-12-24 |
| JP6258921B2 (en) | 2018-01-10 |
| TW201408480A (en) | 2014-03-01 |
| WO2013162238A1 (en) | 2013-10-31 |
| KR101416782B1 (en) | 2014-07-08 |
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Effective date of registration: 20181203 Address after: Seoul, Korea Patentee after: Nex Flexks Co., Ltd. Address before: Seoul, Korea Patentee before: SK INNOVATION Co.,Ltd. |