CN1608835A - Flexible metal foil laminated body - Google Patents
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- CN1608835A CN1608835A CN 200410085678 CN200410085678A CN1608835A CN 1608835 A CN1608835 A CN 1608835A CN 200410085678 CN200410085678 CN 200410085678 CN 200410085678 A CN200410085678 A CN 200410085678A CN 1608835 A CN1608835 A CN 1608835A
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Abstract
Provided is a flexible metal foil laminate which has small dimensional change percentage dispersion by thermal shrinkage and can form a flexible printed circuit board having a fine pitch circuit suitable for mounting a high density pitch IC.In the flexible metal foil laminate which is the laminate of the metal foil and a resin layer, when differential thermal analysis (DSC) is implemented at a temperature increase speed of 10[deg.]C/min in an inert gas, the heat quantity of a heat absorption peak observed in a glass transition region indicates a value of at least 0.5 J/g per unit weight of the resin. The flexible metal foil laminate is obtained by heat treatment at a temperature by 5-50[deg.]C lower than the glass transition temperature Tg of the resin.
Description
Technical field
The present invention relates to flexible metal foil laminated body.More particularly, it is little to the present invention relates to size changing rate and deviation thereof that thermal contraction causes, is suitable as the flexible metal foil laminated body that the baseplate material that forms the pitch circuit uses.
Background technology
In recent years, the high performance of electronic instrument, multifunction, miniaturization develop rapidly, and the miniaturization of the electronic component that uses in the electronic instrument, light-weighted demand increase.Accompany therewith, raw material for electronic component, require each rerum natura such as its hear resistance, mechanical strength, electrology characteristic further to improve, the method for packing of semiconductor element, wiring plate that these elements are installed are also required to have more high density, high function and high-performance.
Particularly be disposed at the LCD on the miniature electric machines such as mobile phone, digital camera, more and more higher meticulous, high-speed driving, therefore it drives with IC and has atomic thin protruding spacing, also requires pitch for the flexible printed wiring substrate that this IC is installed.In order to ensure the driving of pitch reliability, require flexible printed wiring substrate to have high dimensional stability with the coupling part of IC and flexible printed wiring substrate.
Usually; flexible printed wiring substrate carries out photoetch by the flexible metal foil laminated body that the lamilated body by metal forming and resin bed is constituted and forms wiring; with film shape or aqueous カ バ one レ ィ lining and protection wiring, as required portion of terminal is covered etc. with platings such as gold, tin, soldering fluxes and made.The dimensional stability of known flexible printed circuit substrate depends in the flexible metal foil laminated body shrinkage factor mainly as the resin bed of dielectric base.
Resin bed laminated in the flexible metal foil laminated body is mainly formed by polyimide resin, mylar, glass epoxy resin, polyphenylens sulfide resin, liquid crystal polymer etc., and is industrial, if do not require stable on heating purposes, and then the most frequently used inexpensive mylar; If require stable on heating purposes, then the most frequently used polyimide resin.
The polyimide resin that aromatic tetracarboxylic acid dianhydride and aromatic diamine polycondensation obtain is as the extremely excellent polymer of hear resistance and by extensively known.Taked following method in the operation of the metal forming resin multilayer body of making the copper-clad plate representative: the organic solvent solution that makes each raw material of this class react the polyamic acid that obtains is coated on the metal forming, heating makes the solvent evaporation then, finishes the method for polyimides reaction simultaneously; When polyimide resin dissolves in organic solvent, the organic solvent solution of polyimide resin is coated on the metal forming, make the method for solvent evaporation then.Perhaps, the thermoplastic polyimide resin film is contacted with metal forming, form double-sided metal paper tinsel polyimide resin layer zoarium by hot melt knot, this method is industrial applications also.
But these methods all must be through partly being exposed to resin the temperature more than the glass transition temperature Tg, Leng Que operation then.The at this moment residual inevitably lax volume that has quenching to cause, because of the thermal history in the heating process of installation procedure shrinks, this is inevitable.Particularly recently because the fine patterning of flexible printed wiring substrate, people wish the metal forming resin multilayer body that has thermal contraction little, simultaneously also desired temperature to change the change in size that causes little.
Reduce the most method that adopts as the enforcement thermal annealing of putting down in writing among the patent documentation 1-7 of exemplary process of thermal contraction.The common part of these methods is, the heat-treat condition wide ranges that constitutes by heat treatment temperature and heat treatment time, and the kind difference of resin bed in addition, optimum treatment condition is also different certainly, therefore just is defined in the treatment conditions relevant with specific resin naturally.And, can think that heat-treat condition is to regulate according to the molecular structure employing trial and error method of resin, can not illustrate the true clear and definite heat-treat condition that reduces thermal shrinking quantity in theory of having put down in writing.
[patent documentation 1] Japanese kokai publication sho 54-108272 communique
The special fair 07-040636 communique of [patent documentation 2] Japan
[patent documentation 3] Japanese kokai publication hei 09-055567 communique
[patent documentation 4] TOHKEMY 2000-072893 communique
[patent documentation 5] TOHKEMY 2000-202966 communique
[patent documentation 6] TOHKEMY 2001-177200 communique
[patent documentation 7] TOHKEMY 2001-270035 communique
The common point of these prior aries can be enumerated: purpose is to reduce Yin Re and the change in size of the resin that causes part, but except that thermal shrinking quantity, as important characteristic value in the design, can enumerate the deviation of the amount of contraction that thermal conductance causes.About thermal contraction, if the mean value of its amount of contraction is certain, then can obtain according to the size that designs by on design load, carrying out revisal, but the deviation of amount of contraction is when allowable tolerance is above, certainly can't obtain desired dimensional accuracy, therefore, aspect the connection reliability of guaranteeing IC and flexible printed wiring substrate, the deviation of percent thermal shrinkage is important assessment item.But do not cause people's attention as yet for the percent thermal shrinkage deviation at present.
Summary of the invention
The object of the present invention is to provide the deviation of the size changing rate that causes because of thermal contraction little, can form the flexible metal foil laminated body of flexible printed wiring substrate with the pitch circuit that is fit to installation high density pitch IC.
Described purpose of the present invention realizes by flexible metal foil laminated body, in the lamilated body of this metal forming and resin bed, when carrying out differential thermal analysis (DSC) with 10 ℃/minute programming rate in inert gas, the resin that is shown as per unit weight at the heat of the observed endothermic peak in glass transition zone is 0.5J/g or above value.Such flexible metal foil laminated body can obtain by heat-treating under the temperature than low 5-50 ℃ of the glass transition temperature Tg of resin.
The present invention finds: for the size stabilization effect that requires in the manufacturing process that obtains flexible printed wiring substrate or the installation procedure, by under the temperature lower metastable condition resin under the vitreousness being heat-treated than glass transition temperature Tg, make its volume saturated, in other words, carry out the physics ageing, can obtain the most effective effect.
In guaranteeing the heat-treat condition of dimensional stability, the skeleton structure of glass transition temperature Tg and polyimide resin is relevant, but the present invention finds: implementing heat treated effect under than the low temperature of this glass transition temperature Tg is that the size of observed endothermic peak is as the index of dimensional stability (deviation of size changing rate) in the glass transition temperature Tg temperature province when DSC measures.
In order such endothermic peak to occur, by thermal treatment 8 hours or abovely promptly can realize at least under than the temperature of low 5-50 ℃ of glass transition temperature Tg.According to the difference of the kind of polyimide resin, in order to obtain effect of sufficient, need sometimes about 100 hours of heat treatment or more than.Processing time is long more, and near the peak intensity the Tg during DSC measures has the trend of increase, if but laxly fully carry out, then with respect to the processing time, peak intensity reaches capacity.
Usually, the processing time, long then dimensional stability improved, when implementing extreme physics ageing, though the thermal contraction of volume minimizing, on the contrary but energy to failure (integrated value of ss curve) has reduction slightly.Sometimes may consider balance with mechanical properties according to purposes, but in this technology in the scope of application of flexible printed wiring substrate, a little mechanical properties that the physics ageing causes reduces the unlikely level that causes problem that still is in.
Realize that by the physics ageing Stability Analysis of Structuresization of engineering plastics is well-known, but the present invention finds: carry out long heat treatment by this below glass transition temperature Tg, not only the absolute value of percent thermal shrinkage diminishes, and the deviation of percent thermal shrinkage, i.e. 3 σ (σ: standard deviation) also diminish.At the circuit design stage of the flexible printed wiring substrate that requires fine pattern, compared with percent thermal shrinkage itself, its deviation is prior problem, the invention solves this problem.
The 206th page of [non-patent literature 1] Physics and Mechanics of Amorphous Polymers and after (1998)
Near the amount of the absworption peak that occurs the glass transition temperature Tg when implementing to heat up during the Stability Analysis of Structures degree that the physics ageing causes can be measured according to DSC is come it quantitative.The big more then percent thermal shrinkage in this peak is more little, and its deviation also diminishes.Relation between near the glass transition temperature Tg that the physics ageing causes the DSC peak and the reduction effect of dimensional stability and deviation thereof does not depend on the structure of polyimide resin and shows.Even use 2 kinds different or above resin of glass transition temperature Tg, by under temperature, carrying out long heat treatment than low about 5-30 ℃ of glass transition temperature Tg, also can realize the stabilisation of size, but the degree of its effect is subjected to about its processing time, treatment temperature institute.
By such heat treatment, near the heat at the peak that occurs glass transition temperature Tg is big more, and then the size stabilization effect is big more, on the contrary, even carry out long time treatment in the temperature lower than glass transition temperature Tg, the situation that does not observe such peak is arranged also.Such resin can't be expected to realize its size stabilization effect by heat treatment.
Heat treated result shows: near the endothermic peak that glass transition temperature Tg, occurs, heat Δ H show the resin of per unit weight be 0.5J/g or more than, when preferred 2.0J/g or above value, the reduction effect of dimensional stability and deviation thereof is abundant.What is particularly worth mentioning is that such fact: for the few resin material of script thermal shrinking quantity, if enforcement heat treatment makes the peak that can observe the 0.5J/g level, even off-design desired value a little before the heat treatment then, by implementing such heat treatment, also can fall within the technical specification.That is, we can say that it can adopt with other size stabilization method is parallel.
Size stabilization method beyond the heat treating process has the multi-layer coated method of polyimide resin insulating barrier etc., it is industrialization, for so multi-layer resinous, under condition given to this invention, when its resinous principle that shrinks maximum is heat-treated, can reduce heat-shrinkable.
[patent documentation 8] Japanese kokai publication hei 08-250860 communique
[patent documentation 9] Japanese kokai publication hei 09-055567 communique
When flexible printed wiring substrate needed fine wire distribution distance, the polyimide resin film of the tool dimensional stability of the application of the invention can be guaranteed the reliability of coupling part.Particularly owing to introduced heating steps in the bonding operation of anisotropic conductive resin (ACF etc.), if use the polyimide resin that thermal contraction takes place, then connecting portion is offset at the end occurrence positions.Then there is not such problem in the present invention, can be used for the flexible printed wiring substrate of pitch.
Basic means as the heat-shrinkable that can reduce the amorphous resin goods, but not only extensive use, and by heat treated heat shrinkability characteristic being carried out heat analysis, can make the peak intensity of the glass transition temperature Tg part of acquisition become index, effect of the present invention in this can be described as and is with historically new significance.That is, must attempt definite heat-treat condition, and change over and all can set according to the unified mode of considering to any material to every kind of resin material.In addition, can reduce the deviation of epochmaking dimensional stability in the goods design parameter, we can say that this meaning is also very big.
Near the condition of the endothermic peak of the observation glass transition temperature Tg is narrow, does not often observe the situation of endothermic peak under temperature, processing time than low 50 ℃ of glass transition temperature Tg are condition about 10 hours.Put from this, we can say that the present invention has found to realize by heat treatment the specific condition of the situation of size stabilization.
As mentioned above, the present invention has utilized the resin material glass transition temperature Tg not relaxation of lax volume that heat treatment produced under directly, can think that the reason that shows dimensional stability here is as follows: Yin Re and the thermal contraction that produces is derived from the not contraction of lax volume of the amorphous state phase of resin, under glassy state, be removed by the lax of local molecule, and the part of easy contraction is disappeared.
The specific embodiment
Metal forming has electrolytic copper foil, rolled copper foil, aluminium foil, stainless steel foil etc., uses electrolytic copper foil or rolled copper foil usually.Use electrolytic copper foil as the high density flexible printed circuit substrate, because in excellence aspect copper etching formation fine pattern, thereby preferred.These metal formings are used for flexible printed wiring substrate, therefore use the paper tinsel about about 3-35 μ m usually, in order to form the wiring of minuteness space, the paper tinsel of the most about preferred 18 μ m thickness.
The resin bed laminated with these metal forming single or double mainly formed by polyimide resin, mylar etc., preferably uses polyimide resin.These resin beds are with about 5-50 μ m, and the thickness of preferably about 7-25 μ m forms.The thickness of resin bed hereunder, then the reliability at circuit insulation is not enough, mechanical properties such as bending reduce.And be formed on the resin bed of the thickness on this, be easy to generate bubble when then heating, the infringement pliability.
Talk about polyimide resin, structure to polyimide resin is not particularly limited, all can obtain effect, but with as 270 ℃ of these temperature of the heat resisting temperature of the desired unleaded solder of flexible printed wiring substrate with uses anisotropic conductive adhesive (ACF) to be the prerequisite consideration, then preferably the glass transition temperature Tg of polyimide resin be 290 ℃ or more than.Need not consider under the stable on heating situation of solder flux that glass transition temperature Tg is 240 ℃ or above getting final product.And when considering thermal welding, solvent seasoning step, resin thermal decomposition etc., then preferred glass transition temperature T g is 350 ℃ or following.Heat-treat for a long time under this temperature province, the aerobic existence then can go wrong, and is to heat-treat under the medium anaerobic state of inert gas more substantially therefore.
For making glass transition temperature Tg in 290-350 ℃ of scope, the copolymerization composition that constitutes the monomer of polyimide resin is a problem, considers hear resistance, can use the aromatic tetracarboxylic acid dianhydride as acid anhydrides.Described aromatic tetracarboxylic acid dianhydride for example has pyromellitic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl tetracarboxylic dianhydride, isopropylidene two (the inferior phenoxy group of 4--4-phthalic acid) dianhydride, 2,2 '-two (3,4-dicarboxyl phenyl) propane dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 3,4,9, the 10-perylenetetracarboxylic dianhydride, two (3, the 4-carboxyl phenyl) ether dianhydride, naphthalene-1,2,4, the 5-tetracarboxylic dianhydride, naphthalene-1,4,5, the 8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5, the 8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydro naphthalene-1,2,5, the 6-tetracarboxylic dianhydride, 2,6-naphthalene dichloride-1,4,5, the 8-tetracarboxylic dianhydride, 2,7-naphthalene dichloride-1,4,5, the 8-tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetrachloride-1,4,5, the 8-tetracarboxylic dianhydride, luxuriant and rich with fragrance-1,8,9, the 10-tetracarboxylic dianhydride, 2,2-two (2,3-dicarboxyl phenyl) ethane dianhydride, 1,1-two (3,4-dicarboxyl phenyl) ethane dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, benzene-1,2,3, the 4-tetracarboxylic dianhydride, 3,4,3 ', 4 '-benzophenone tetracarboxylic dianhydride etc. can be separately or use as 2 kinds or above mixture.
For example have 4 with the aromatic diamine of these aromatic tetracarboxylic acid dianhydride's reactions, 4 '-diamino-diphenyl ether, m-phenylene diamine (MPD), p-phenylenediamine (PPD), 4,4 '-diamino-diphenyl propane, 4,4 '-diaminodiphenyl-methane, benzidine, 4,4 '-diaminourea diphenyl sulfide, 4,4 '-DADPS, 3,3 '-DADPS, 2, the 6-diamino-pyridine, two (4-aminophenyl) diethylsilane, two (4-aminophenyl) diphenyl silane, 3,3 '-dichloro-benzidine, two (4-aminophenyl) ethyl phosphine oxide, two (4-aminophenyl) phenyl phosphine oxide, two (4-aminophenyl)-N-aniline, two (4-aminophenyl)-N-methylamines, 1, the 5-diaminonaphthalene, 3,3 '-dimethyl-4,4 '-benzidine, 3,4 '-dimethyl-3 ', the 4-benzidine, 3,3 '-dimethoxy benzidine, 2,4-two (beta-amino-tert-butyl group) toluene, two (right-beta-amino-tert-butyl-phenyl) ether, right-two (2-methyl-4-aminobenzyl) benzene, right-two (1,1-dimethyl-5-aminobenzyl) benzene, m-xylene diamine, the paraxylene diamines, 1,3-diaminourea adamantane, 3,3 '-diaminostilbene, 1 '-two adamantane, 3,3 '-diaminostilbene, 1 '-two adamantane, two (to aminocyclohexyl) methane, hexamethylene diamine, the heptamethylene diamines, eight methylene diamine, nine methylene diamine, decamethylene diamine, 3-methyl heptamethylene diamines, 4,4,-dimethyl heptamethylene diamines, 2,11-diaminourea dodecane, 1,2-two (the amino propoxyl group of 3-) ethane, 2, the 2-dimethylated propyl diethylenetriamine, 3-methoxyl group-hexamethylene diamine, 2,5-dimethyl hexamethylene diamine, 5-methyl nine methylene diamine, 5-methyl nine methylene diamine, 1, the 4-DACH, 1,12-diaminourea octadecane, 2, the 5-diaminostilbene, 3, the 4-oxadiazole, 2,2-two (4-aminophenyl) HFC-236fa, N-(3-aminophenyl)-4-aminobenzamide, 4-aminophenyl-3-Aminobenzoate, 6-amino-2-(p-aminophenyl) benzimidazole etc., they can be separately or use as 2 kinds or above mixture, preferred use 4 separately, 4 '-diamino-diphenyl ether.
The above-mentioned polycondensation reaction of carrying out with 1: 1 mol ratio between the two not necessarily needs polymerization catalyst, but in order to control reactivity, can use tertiary amines.The example of tertiary amines has trimethylamine, triethylamine, pyridine, isoquinolin, 2-ethylpyridine, 2-picoline, N-ethylmorpholine, N-methylmorpholine, N; N-diethyl cyclohexylamine, N; N-dimethyl cyclohexyl amine, 4-benzoyl pyridine, 2,4-lutidine, 2,6-lutidine, 2; 4; 6-collidine, 3,4-lutidine, 3,5-lutidine, 4-picoline, 3-picoline, 4-isopropyl pyridine, N; N-dimethyl benzylamine, 4-benzyl pyridine, N, N-dimethyl dodecyl amine etc.
Polycondensation reaction can be with an organic solvent, N is for example arranged, dinethylformamide, N, N-dimethylacetylamide, N, N-DEF, N, N-diethyl acetamide, N-dimethyl methoxy yl acetamide, N-methyl caprolactam, dimethyl sulfoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl phosphoramide, sulfolane, formamide, N-NMF, butyrolactone etc., they can be separately or use as 2 kinds or above mixture.These organic solvents can also be used in combination with the solvent of benzene,toluene,xylene, cyclohexane, benzonitrile, diox equal solvent difference.
The one-level product of polycondensation reaction is the precursor of polyimide resin a---polyamic acid, uses apparatus for coating that this amic acid solution (it can be a reaction product solution itself) is applied on the metal forming.Apparatus for coating can use gravure roll coating machine, reverse roll coater, coiling rod reverse roll coater, the excellent coating machine that winds the line, knife type coater, curtain stream coating machine, mold pressing coating machine, multilayer film to press coating machine etc., but to improve characteristic etc. is purpose, can divide multiple polyamic acid solution multi-layer coated.Perhaps also can adopt and make polyimide resin film, it be sticked on method on the metal forming with binding agent by polyamic acid.
In the pitch purposes, adopted and do not used binding agent and the method for polyimide resin is direct and metal forming bonding.Metal formings such as described and Copper Foil show that good close-burning polyimide resin has, by (A) isopropylidene two (4-inferior phenoxy group-4-phthalic acid) dianhydride and (B) 3,3 ', 4, this polyimide resin of copolymer of 2 kinds of aromatic tetracarboxylic acid dianhydrides that 4 '-benzophenone tetracarboxylic dianhydride constitutes and (C) 6-amino-2-(p-aminophenyl) benzimidazole etc.
[patent documentation 10] WO 01/29136 A1
In addition, can not use binding agent, use the direct and metal forming bonding via the synthetic polyimide resin of polyamic acid, wherein said polyimide resin can exemplify following material.
By (A) pyromellitic acid dianhydride and (B) 3,3 ', 4, the 2 kinds of tetracarboxylic dianhydrides that 4 '-benzophenone tetracarboxylic dianhydride constitutes and (C) copolymer of 6-amino-2-(p-aminophenyl) benzimidazole,
By (A) isopropylidene two (4-inferior phenoxy group-4-phthalic acid) dianhydride and (B) 3,3 ', 4, the 2 kinds of tetracarboxylic dianhydrides that 4 '-biphenyl tetracarboxylic dianhydride constitutes and (C) copolymer of 6-amino-2-(p-aminophenyl) benzimidazole,
By (A) isopropylidene two (4-inferior phenoxy group-4-phthalic acid) dianhydride and (B) 3,3 ', 4,2 kinds of tetracarboxylic dianhydrides that 4 '-biphenyl tetracarboxylic dianhydride constitutes with by (C) 6-amino-2-(p-aminophenyl) benzimidazole and (D) two (4-aminophenyl) ether (D
1) and phenylenediamine (D
2) in the copolymer of 2 kinds or 3 kinds diamines of at least a formation.
Polyimide resin or its precursor that can also be coated with agent of low hygroscopicity or low heat expansion on the good polyimide resin layer of above-mentioned and metal forming caking property are polyamic acid.Have as above to be exemplified via the synthetic polyimide resin of polyamic acid.
In addition, thermoplastic polyimide resin is contacted with metal forming, by the method industrialization of thermal welding formation double-sided metal paper tinsel polyimide resin layer zoarium, such method is also applicable.In addition, so long as can obtain the method for the lamilated body of metal forming and polyimide resin, all applicable the present invention.
At this moment, with the control line coefficient of expansion, to regulate mechanical property, improve caking property etc. be purpose, also can use the blend of different polyimide resins or different types of resin alloy is used.In addition, be purpose with the improvement of various characteristics, can mix inanimate matter, organic matter or uses such as metallic powder, fiber, for preventing the oxidation of metal foil conductor, can also add antioxidant, or be purpose, can add and use silane coupler etc. to improve caking property.
Make metal forming/resin bed lamilated body, preferably copper foil/polyimide resin bed lamilated body (polyimide resin copper-clad plate) by above-mentioned arbitrary method, then with resin bed than low about 5-50 ℃ of glass transition temperature Tg, preferably under about 10-30 ℃ the temperature, about at least 8 hours of heat treatment under blanket of nitrogen.At this moment, copper-clad plate can be the coiled material shape, can be one sheet also, but consider batch process, preferably heat-treats with the coiled material shape.Use vacuum drying oven to replace atmosphere of inert gases, also can obtain same effect, but under the situation of considering heat transfer rate, use the inert gas baking oven more appropriate.
For improving heat transfer efficiency, can shorten the time that goods integral body reaches design temperature by on the fulcrum that supports coiled material, introducing auxiliary heater etc.Heat treatment time is long, and then extension at break can reduce, and measures but proceed to by the differential thermal analysis after the heat treatment (DSC), when heating up with 10 ℃/minute programming rates, produces endothermic peak in the temperature province of glass transition temperature Tg.Under temperature, handle, can not obtain stable structure sometimes near glass transition temperature Tg.Heat treated result is, measures when heating up by DSC, when the heat of the endothermic peak that produces in the temperature province that observes glass transition temperature Tg is that the resin of per unit weight is 0.5J/g or when above, can confirm to have the effect of size stabilization.
As necessary heat treatment temperature of heat-treat condition and heat treatment time, its kind with resin is relevant, heat treatment time be generally about 8 hours or more than, preferably in about 24 hours-120 hours scope, can obtain big effect.Can cause cost to rise than this longer heat treatment time, thereby be unpractical, can not ignore the thermal decomposition of resin in addition for industrialization.But, under the situation of almost not seeing the resin thermal decomposition, the processing time, the longer the better.
Under the situation that resin is made of multiple composition, for example is that resin bed is the blend or the situation of multi-layer tectosome accordingly, even only the main component of the resin that constituted is carried out the physics ageing, also can obtain effect sometimes.In addition, the glass transition temperature Tg of resin is roughly the same, and then the effect of size stabilization is also big.And, heat-treat according to the glass transition temperature Tg that constitutes the high side of resin, continue afterwards under the temperature lower, to heat-treat than glass transition temperature Tg, i.e. heat treatment of so-called multistage also is effective.
After heat treatment finished, the size of measuring lamilated body was as a reference value.Measure to adopt following method to carry out: the lamilated body sheet of 200 * 250mm size was placed 20 ℃, the constant temperature and humidity cabinet of 65%RH 24 hours, on the lamilated body sheet, beats the hole of diameter 1mm then at interval, make a call to 20 holes altogether with 50mm, measure the hole in the heart distance.Then be defined as the MD direction along coating direction detection size, then be defined as the TD direction along the direction detection vertical with the coating direction.
Afterwards, carry out the copper etching, in 20 ℃, the constant temperature and humidity cabinet of 65%RH, kept 24 hours, similarly carry out the mensuration of size then with surface processing devices such as etching machines.Then,, in 20 ℃, the constant temperature and humidity cabinet of 65%RH, kept 24 hours then, similarly carry out the mensuration of size then 200 ℃ of down heating 30 minutes.During deisgn product, the problem of heating back dimensional discrepancy is very important, and terminal pitch is 40 μ m or when following, preferably in standard deviation, the value of 3 σ be 0.05% or below.
Among the present invention, can unite use with other size stabilization methods.That is,,, can easily obtain the dimensional stability of target thus by physics ageing implementation structure stabilisation in dimensional stability that obtains by additive method (percent thermal shrinkage and deviation thereof) and the also poor a little occasion of specification requirement etc.
Particularly after the copper-clad plate of having purchased commercially available product, heat-treating under low about 10 ℃ temperature than the glass transition temperature Tg of measuring by DSC, heat-treat according near the mode of carrying out glass transition temperature Tg, producing when DSC heat up to measure endothermic peak, can suppress the deviation of dimensional stability like this.
About heat treated result, when near the heat of the endothermic peak that is occurring the glass transition temperature Tg show the resin of per unit weight be 0.5J/g or more than, when preferred 2.0J/g or above value, can confirm dimensional stability clearly and reduce the effect of deviation.But, will be exposed to glass transition temperature or above following time of temperature, then lose the size stabilization effect through the stable product of Overheating Treatment, size.
The mensuration of the heat of this endothermic peak (caloric receptivity) Δ H is to be undertaken by the differential thermal analysis of implementing in inert gas, under the condition of 10 ℃/minute of programming rates (DSC), be used to calculate the baseline of the peak area of the endothermic peak that in the temperature province of glass transition temperature Tg, observes this moment, be base line extension with high temperature side in the temperature province of glass transition temperature Tg and use, by with glass transition temperature Tg under the peak that intersection point surrounded, that be derived from the volume relaxation phenomenon of DSC curve calculate.As the DSC test sample, can keep metal forming to adhere to and measure, the weight of resin bed part has adopted the method that is converted by the weight difference before and after the etching.
Embodiment
Below, according to embodiment the present invention is described.
Embodiment 1
For copper-clad plate (the chemicals ェ ス パ ネ ッ of Nippon Steel Network ス KE),, in nitrogen stream,, it is 345 ℃ with its glass transition temperature Tg of determination of heating rate of 10 ℃/minute by DSC.Under blanket of nitrogen, 330 ℃ of heat treatments 72 hours, the heat absorption enthalpy that the glass transition temperature place after heat treatment observes is 0.55J/g with this coiled material shape copper-clad plate.The weight ratio of copper and resin is determined by the weight ratio before and after the etching, is converted into the value of per unit weight resin.
After the heat treatment, sheet is cut in the gained copper-clad plate, measures caloric receptivity Δ H, accumulated size rate of change (total shrinkage) under the glass transition temperature, calculating mean value and dispersion value 3 σ.Not remove the state estimating sample of Copper Foil, carry out etching after the mensuration, to remove dry weight behind the copper as weight resin.
Δ H: the DSC7 that uses パ-キ Application ェ Le マ-company to make, carrying out DSC with 10 ℃/minute programming rates measures, be used to calculate the baseline of the peak area of the endothermic peak that in the temperature province of glass transition temperature Tg, observes this moment, be base line extension with high temperature side in the temperature province of glass transition temperature Tg and use, by with glass transition temperature Tg under the peak that intersection point surrounded, that be derived from the volume relaxation phenomenon of DSC curve calculate.
Total heat shrink rate: IPC-TM-650 2.2.4 Revision C (method C)
But this is the rate of change when exposing temperature change to the open air and be 200 ℃
Comparative example 1
Among the embodiment 1, measure the preceding total heat shrink rate of copper-clad plate under 200 ℃ of heat treatment.
Embodiment 2
For copper-clad Kapton (clock deep pool chemicals ァ ピ カ Le NPI),, in nitrogen stream,, it is 348 ℃ with its glass transition temperature Tg of determination of heating rate of 10 ℃/minute by DSC.Under blanket of nitrogen, 330 ℃ of heat treatments 72 hours, the heat absorption enthalpy that the glass transition temperature place after heat treatment observes is 0.61J/g with this coiled material shape copper-clad plate.The weight ratio of copper and resin is determined by the weight ratio before and after the etching, is converted into the value of per unit weight resin.Be determined at the total heat shrink rate under 200 ℃ after the heat treatment under this blanket of nitrogen.
Comparative example 2
Among the embodiment 2, measure the preceding total heat shrink rate of copper-clad plate under 200 ℃ of heat treatment.
As shown in table 1 below by the result that above each embodiment and comparative example obtain.
Table 1
Δ H measures
Total shrinkage (%)
Heat-treat condition
(J/g)
Direction
On average
3 σ
Embodiment 1 0.55 TD-0.02 0.02
330 ℃ (Tg-15 ℃), 72 hours MD-0.03 0.02
Comparative example 1 0.0 TD-0.05 0.03
(being untreated) MD-0.06 0.04
Embodiment 2 0.61 TD-0.00 0.03
330 ℃ (Tg-18 ℃), 72 hours MD-0.00 0.03
Comparative example 2 0.0 TD-0.04 0.06
(being untreated) MD-0.04 0.06
Embodiment 3
With roll-coater with isopropylidene two (4-inferior phenoxy group-4-phthalic acid) dianhydride (mol ratio 0.4), 3,3 ', 4, the N-N-methyl-2-2-pyrrolidone N-varnish solution of the polyimide resin that 4 '-benzophenone tetracarboxylic dianhydride (mol ratio 0.6) and 6-amino-2-(p-aminophenyl) benzimidazole (mol ratio 1.00) copolymerization obtain (the solid shape branch concentration 14 weight % of polymer) is coated on the Copper Foil of 1/2 ounce (18 μ m) with the thickness of 1/2 mil (12.7 μ m).
With this Copper Foil/polyimide resin (305 ℃ of Tg) laminate under oxygen concentration 0.5% or following environment with 390 ℃ of dryings of maximum temperature.Dried solvent is 0.4 weight %.Slowly after the cooling, the coiled material that batches is packed in the nitrogen baking oven, processing time, temperature are carried out various changes, heat-treat.
After the heat treatment, sheet is cut in the gained copper-clad plate, measures the caloric receptivity Δ H under the glass transition temperature similarly to Example 1.
The result that embodiment 3 obtains is shown in the curve map of Fig. 1.This figure shows, treatment temperature is during more near Tg, and the caloric receptivity Δ H glass transition temperature under obviously increases at short notice, shows for the time with practicality to heat-treat preferably about Tg-15 ℃.
Description of drawings
Fig. 1 is the curve map of Δ H and heat treatment temperature and time relation among the expression embodiment 3.
Fig. 2 is the schematic sectional view of the state of expression when IC is installed on FPC.
Symbol description:
1 resin bed (substrate film)
2?FPC
3 terminals
4 projectioies
5?IC
Claims (3)
1. flexible metal foil laminated body, this flexible metal foil laminated body is the lamilated body of metal forming and resin bed, when in inert gas, carrying out differential thermal analysis, show that at the heat of the observed endothermic peak in glass transition zone the resin of per unit weight is 0.5J/g or above value with 10 ℃/minute programming rate.
2. the flexible metal foil laminated body of claim 1, this flexible metal foil laminated body is the lamilated body of metal forming and resin bed, heat-treats under the temperature than low 5-50 ℃ of the glass transition temperature Tg of resin.
3. claim 1 or 2 flexible metal foil laminated body, wherein the resin bed of flexible metal foil laminated body is the polyimide resin with glass transition temperature Tg of 290-350 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP357738/2003 | 2003-10-17 | ||
| JP2003357738A JP4731107B2 (en) | 2003-10-17 | 2003-10-17 | Flexible metal foil laminate |
| JP357738/03 | 2003-10-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1608835A true CN1608835A (en) | 2005-04-27 |
| CN1608835B CN1608835B (en) | 2010-04-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410085678 Expired - Fee Related CN1608835B (en) | 2003-10-17 | 2004-10-15 | Flexible metal foil laminated body |
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| Country | Link |
|---|---|
| JP (1) | JP4731107B2 (en) |
| CN (1) | CN1608835B (en) |
| TW (1) | TW200514685A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017209060A1 (en) | 2016-06-03 | 2017-12-07 | 株式会社有沢製作所 | Method for producing flexible metal-clad laminate |
| CN115353845B (en) * | 2022-08-26 | 2024-02-02 | 江西省航宇电子材料有限公司 | Stainless steel-based copper-clad plate silk-screen insulating adhesive and silk-screen printing method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3805546B2 (en) * | 1998-11-09 | 2006-08-02 | 株式会社カネカ | Manufacturing method of heat-resistant bonding sheet |
| JP4507137B2 (en) * | 1999-12-17 | 2010-07-21 | 東洋紡績株式会社 | Flexible printed wiring board and manufacturing method thereof |
| JP3494098B2 (en) * | 1999-12-20 | 2004-02-03 | ソニーケミカル株式会社 | Flexible printed circuit board |
| TW584596B (en) * | 2001-12-10 | 2004-04-21 | Mitsui Chemicals Inc | Method for manufacturing a polyimide and metal compound sheet |
-
2003
- 2003-10-17 JP JP2003357738A patent/JP4731107B2/en not_active Expired - Fee Related
-
2004
- 2004-09-14 TW TW093127755A patent/TW200514685A/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI343869B (en) | 2011-06-21 |
| JP2005119178A (en) | 2005-05-12 |
| TW200514685A (en) | 2005-05-01 |
| CN1608835B (en) | 2010-04-28 |
| JP4731107B2 (en) | 2011-07-20 |
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