CN1943285A - Laminate for wiring board - Google Patents
Laminate for wiring board Download PDFInfo
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- CN1943285A CN1943285A CNA200580005515XA CN200580005515A CN1943285A CN 1943285 A CN1943285 A CN 1943285A CN A200580005515X A CNA200580005515X A CN A200580005515XA CN 200580005515 A CN200580005515 A CN 200580005515A CN 1943285 A CN1943285 A CN 1943285A
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- China
- Prior art keywords
- polyimide resin
- laminate
- resin layer
- dianhydride
- tetracarboxylic acid
- Prior art date
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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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Laminated Bodies (AREA)
Abstract
本发明涉及具有聚酰亚胺树脂层作为绝缘层的线路板用积层体，所述聚酰亚胺树脂层具有高耐热性、低吸湿性，并且尺寸热稳定性也优异，不伴有来自于粘接层的诸问题，能够抑制湿度产生的翘曲，而且在TD方向和MD方向上的湿度膨胀系数的差小，在面内无各向异性。该线路板用积层体在聚酰亚胺树脂层的单面或双面上具有金属箔，上述聚酰亚胺树脂层的至少1层含有大于等于10摩尔％的由2，2’－二烷氧基联苯胺或2，2’－二苯氧基联苯胺和四羧酸酐得到的聚酰亚胺结构单元。The present invention relates to a laminate for wiring boards having a polyimide resin layer as an insulating layer, the polyimide resin layer has high heat resistance, low moisture absorption, and is also excellent in dimensional thermal stability without accompanying Various problems from the adhesive layer can suppress warpage due to humidity, and the difference in the coefficient of humidity expansion between the TD direction and the MD direction is small, and there is no anisotropy in the plane. The laminate for circuit boards has metal foil on one or both sides of the polyimide resin layer, at least one of the above polyimide resin layers contains 10 mol% or more of 2,2'-bis A polyimide structural unit obtained from alkoxybenzidine or 2,2'-diphenoxybenzidine and tetracarboxylic anhydride.
Description
Technical field
The present invention relates to be used for the laminate for wiring board of flexibility printed circuit board, HDD draft hitch (suspension) etc.
Background technology
In recent years the high performance of electronic equipment, multifunction and miniaturization develops rapidly, accompanies for the electronic component that is used for electronic equipment, their substrate is installed with it, and requiring of densification, high performance is surging.About flexibility printed circuit board (hereinafter referred to as FPC), will for the material that constitutes FPC, also more and more be strict with slimming and dimensional stability to carrying out development such as fine rule processing, multilayer formation.
The widely-used film that is made of the polyimide resin of all excellents of the dielectric film of common FPC, dielectric film and intermetallic insulation adhesive linkage use epoxy resin, the acrylic resin of low-temperature processability excellence.But there is the problem that causes thermal endurance, size thermal stability to descend in these adhesive linkages.
In order to address this problem, adopted the method that does not form adhesive linkage and on metal, directly be coated with the formation polyimide resin layer recently.Special fair 6-93537 communique discloses by making the polyimide resin layer multiple stratification that thereby the method for the FPC of bonding force and size excellent heat stability is provided with the different multiple polyimides of thermal coefficient of expansion.But, because the moisture absorption of these polyimides is big, cause the problems such as bad connection that change in size produces after bulging when impregnated in solder bath, the moisture absorption that fine rule adds man-hour, in addition, because the humidity expansion coefficient that is generally used for the metal of conductor is 0 or near 0, thus the change in size after the moisture absorption also become laminate warpage, curl, the reason of rough sledding such as distortion.
As document formerly related to the present invention following document is arranged.
Patent documentation 1: special fair 6-93537 communique
Patent documentation 2: the spy opens flat 2-225522 communique
Patent documentation 3: the spy opens the 2001-11177 communique
Patent documentation 4: the spy opens flat 5-271410 communique
Because such background, to requiring surgingly, therefore the polyimides that is used for it various improvement researchs have been carried out in recent years by what have the polyimide resin of dimensional stability constitutes after excellent agent of low hygroscopicity, the moisture absorption a FPC.For example, thereby the spy opens and has proposed in flat 2-225522 communique and the Te Kai 2001-11177 communique to increase but have manufacturing cost by introducing the polyimides that fluorine resin improves hydrophobicity and presents agent of low hygroscopicity, with the shortcoming of the cementability difference of metal material.For the combination of in addition low moisture absorptionization, open shown in the flat 5-271410 communique etc. as the spy, can not in the superperformance that polyimides such as keeping high-fire resistance, low thermal coefficient of expansion has, realize agent of low hygroscopicity.
Polyimides has the dicarboxylic acids composition and replaces the structure that combines with two amine components, though the spy opens the 2001-11177 communique, the spy opens to exemplify out in the flat 5-271410 communique as diamines and uses benzidine, its benzidine class that is replaced by methoxyl group, but do not enumerate its concrete example, can not predict what kind of characteristic these have.
Summary of the invention
Therefore, the objective of the invention is to address the above problem, the laminate for wiring board with polyimide layer is provided, described polyimide layer has excellent thermal endurance, size thermal stability, and has realized agent of low hygroscopicity.
The present invention relates to laminate for wiring board, this laminate has metal forming on the single or double of polyimide resin layer, it is characterized in that: at least 1 layer of above-mentioned polyimide resin layer contains more than or equal to construction unit shown in the following general formula (1) of 10 moles of %.
(in the formula, Ar
1Be the organic group with 4 valencys of one or more aromatic rings, R is C
1-6Alkyl).
Laminate for wiring board of the present invention has the structure of stacked metal forming on the single or double of one or more layers polyimide resin layer.At least 1 layer of polyimide resin layer contains more than or equal to the construction unit shown in the above-mentioned general formula (1) of 10 moles of %.
In the construction unit shown in the general formula (1), in the formula, Ar
1Be the organic group of 4 valencys, can be called the aromatic tetracarboxylic acid's residue that generates by aromatic tetracarboxylic acid or its acid dianhydride etc. with one or more aromatic rings.Therefore, by being described, the aromatic tetracarboxylic acid who uses understands Ar
1Usually, synthesize when having the polyimides of said structure unit, owing to use the situation of aromatic tetracarboxylic acid's dianhydride in the majority, the following aromatic tetracarboxylic acid's dianhydride that uses is to preferred Ar
1Describe.
Do not have particular determination as above-mentioned aromatic tetracarboxylic acid's dianhydride, can use known aromatic tetracarboxylic acid's dianhydride.If enumerate concrete example, then can enumerate pyromellitic acid anhydride, 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-the benzophenone tetracarboxylic acid dianhydride, 2,3,3 ', 4 '-the benzophenone tetracarboxylic acid dianhydride, naphthalene-2,3,6, the 7-tetracarboxylic acid dianhydride, naphthalene-1,2,5, the 6-tetracarboxylic acid dianhydride, naphthalene-1,2,4, the 5-tetracarboxylic acid dianhydride, naphthalene-1,4,5, the 8-tetracarboxylic acid dianhydride, naphthalene-1,2,6, the 7-tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydro naphthalene-1,2,5, the 6-tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydro naphthalene-2,3,6, the 7-tetracarboxylic acid dianhydride, 2,6-dichloronaphtalene-1,4,5, the 8-tetracarboxylic acid dianhydride, 2,7-dichloronaphtalene-1,4,5, the 8-tetracarboxylic acid dianhydride, 2,3,6,7-Tetrachloronaphthalene-1,4,5, the 8-tetracarboxylic acid dianhydride, 1,4,5,8-Tetrachloronaphthalene-2,3,6, the 7-tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, 3,3 "; 4,4 " para-terpheny tetracarboxylic acid dianhydride, 2,2 "; 3,3 " para-terpheny tetracarboxylic acid dianhydride, 2,3,3 ", 4 " para-terpheny tetracarboxylic acid dianhydrides, 2,2-two (2,3-dicarboxyl phenyl) propane dianhydride, 2, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2-, two (2,3-dicarboxyl phenyl) ether dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) methane dianhydride, two (2,3-dicarboxyl phenyl) sulfone dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 1,1-two (2,3-dicarboxyl phenyl) ethane dianhydride, 1, two (3,4-dicarboxyl phenyl) the ethane dianhydride perylenes-2 of 1-, 3,8,9-tetracarboxylic acid dianhydride perylene-3,4,9,10-tetracarboxylic acid dianhydride perylene-4,5,10,11-tetracarboxylic acid dianhydride perylene-5,6,11, the 12-tetracarboxylic acid dianhydride, luxuriant and rich with fragrance-1,2,7, the 8-tetracarboxylic acid dianhydride, luxuriant and rich with fragrance-1,2,6, the 7-tetracarboxylic acid dianhydride, luxuriant and rich with fragrance-1,2,9, the 10-tetracarboxylic acid dianhydride, pentamethylene-1,2,3, the 4-tetracarboxylic acid dianhydride, pyrazine-2,3,5, the 6-tetracarboxylic acid dianhydride, pyrrolidines-2,3,4, the 5-tetracarboxylic acid dianhydride, thiophene-2,3,4, the 5-tetracarboxylic acid dianhydride, 4,4 '-the two O-phthalic acid dianhydrides of oxygen etc.In addition, these can use separately or 2 kinds or multiple mixing are used.
Wherein, be preferably selected from pyromellitic acid anhydride (PMDA), naphthalene-2,3,6,7-tetracarboxylic acid dianhydride (NTCDA) and 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA).In order to realize low thermal coefficient of expansion, especially preferably use PMDA or NTCDA.By mix using the BPDA of appropriate amount therein, can be adjusted to and the thermal coefficient of expansion of metal forming with degree, can be adjusted to the practical desired value smaller or equal to 20ppm/ ℃ that.Can suppress the warpage of laminate, the generation of curling etc. like this.These aromatic tetracarboxylic acid's dianhydrides also can with other aromatic tetracarboxylic acid's dianhydride and usefulness, but should make its use amount be whole aromatic tetracarboxylic acid's dianhydrides more than or equal to 50 moles of %, be preferably greater than and equal 70 moles of %.That is, during tetracarboxylic dianhydride's selection, the tetracarboxylic dianhydride of the characteristic that the preferred concrete thermal coefficient of expansion of selecting to be suitable for to embody the polyimides that the polymerization heating obtains and application targets such as heat decomposition temperature, glass transition temperature are required.
The diamines that uses as essential composition in the polyimide resin that uses in the present invention synthetic is the aromatic diamine shown in the following general formula (2).
In the formula, R has the identical meaning of R with general formula (1), is C
1-6Alkyl, but C preferably
1-4Alkyl or C
6Aryl.Be more preferably ethyl and n-pro-pyl or phenyl.
The polyimide resin that uses among the present invention can make aromatic tetracarboxylic acid's dianhydride and contain more than or equal to the diamine reactant of aromatic diamine shown in the above-mentioned general formula (2) of 10 moles of % and advantageously make.
In the present invention, when stating aromatic diamine shown in the general formula (2) in the use, can become the polyimides of copoly type like this to use its other diamines in addition smaller or equal to the ratio of 90 moles of %.
Construction unit shown in the general formula (1) can contain 10～100 moles of % at least in 1 layer of polyimide resin layer, preferred 50～100 moles of %, more preferably 70～100 moles of %, further preferred 90～100 moles of %.
As other the diamines beyond the aromatic diamine shown in the general formula (2), there is not particular determination, if for example, can enumerate 4, the 6-dimethyl-m-phenylenediamine, 2, the 5-dimethyl-p-phenylenediamine, 2,4-diaminourea , 4,4 '-methylene two (ortho-aminotoluene), 4,4 '-methylene two-2, the 6-xylidine, 4,4 '-methylene-2, the 6-diethylaniline, 2, the 4-toluenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), 4,4 '-diamino-diphenyl propane, 3,3 '-diamino-diphenyl propane, 4,4 '-diamino-diphenyl ethane, 3,3 '-diamino-diphenyl ethane, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 4,4 '-the diamino-diphenyl thioether, 3,3 '-the diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, benzidine, 3,3 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy benzidine, 4,4 '-the diaminourea para-terpheny, 3,3 '-the diaminourea para-terpheny, bis(p-aminocyclohexyl)methane, two (right-the beta-amino tert-butyl-phenyl) ether, two (right-Beta-methyl-δ-amino amyl group) benzene, right-two (the amino amyl group of 2-methyl-4-) benzene, right-two (1, the amino amyl group of 1-dimethyl-5-) benzene, 1, the 5-diaminonaphthalene, 2, the 6-diaminonaphthalene, 2, two (the beta-amino tert-butyl group) toluene of 4-, 2, the 4-diaminotoluene, meta-xylene-2, the 5-diamines, paraxylene-2, the 5-diamines, m-xylene diamine, the p dimethylamine, 2, the 6-diamino-pyridine, 2, the 5-diamino-pyridine, 2,5-diaminostilbene, 3,4- diazole, piperazine, 3,4,4 '-the triamido diphenyl ether, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-two (4-amino-benzene oxygen) biphenyl etc.
Wherein, preferably use 4,4 '-diamino-diphenyl ether (DAPE), 1, two (4-amino-benzene oxygen) benzene (TPE-R) of 3-, p-phenylenediamine (PPD) (p-PDA), 2,2 '-dimethyl-4,4 '-benzidine (m-TB) etc.In addition, when using these diamines, its preferred usage ratio is 0～50 mole of % of whole diamines, the more preferably scope of 0～30 mole of %.
As the polyamic acid of polyimide resin precursor, can adopt with 0.9～1.1 mol ratio and use aromatic diamine composition and aromatic tetracarboxylic acid's two anhydride components shown in above-mentioned, the known method of polymerization is made in organic polar solvent.That is, by under nitrogen current, making aromatic diamine be dissolved in N, in the organic solvents such as N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-after, add aromatic tetracarboxylic acid's dianhydride, at room temperature react about 3～4 hours and make.At this moment, molecular end can be used aromatic series monoamine or dicarboxylic anhydride end-blocking.
When use contains aromatic tetracarboxylic acid's two anhydride components of naphthalene skeleton, for example, after under nitrogen current, making the aromatic diamine composition be dissolved in metacresol, add catalyst and aromatic tetracarboxylic acid's two anhydride components, heating about 190 ℃ about 10 hours, then after returning room temperature, make its reaction about 8 hours again and make.
Use spreader will be coated on by the polyamic acid solution that above-mentioned reaction makes as on the metal forming of support or on the adhesive linkage that forms on the metal forming, adopt hot-imide method or chemical imidizate method to carry out imidizate, obtain laminate for wiring board of the present invention.Hot-imide is by after predrying 2～60 minutes under smaller or equal to 150 ℃ temperature, usually in heat treatment under the temperature about 130～360 ℃ about 2～30 minutes and carry out.The chemistry imidizate is to be undertaken by adding dehydrating agent and catalyst in polyamic acid.As employed metal forming, preferred Copper Foil or SUS paper tinsel, its preferred thickness range is smaller or equal to 50 μ m, 5～40 μ m are favourable.Copper thickness is thin to be suitable for forming fine pattern, from this viewpoint, and the scope of preferred 8～15 μ m.
Polyimide resin layer can be that individual layer also can be a multilayer.During for the polyimide resin layer of multilayer, by being coated with polyamic acid solution and dry operation repeatedly, heat-treat then to remove and desolvate, so at high temperature to its carry out heat except and make its imidizate, can form the polyimide based resin layer of sandwich construction.At this moment, the scope of preferred 3～75 μ m of the gross thickness of the polyimide resin layer of formation.When being multilayer, wherein at least 1 layer is necessary for containing polyimide resin layer more than or equal to construction unit shown in the general formula (1) of 10 moles of % (below be also referred to as this polyimide resin layer), its thickness should be polyimide resin layer integral body more than or equal to 30%, be preferably more than and equal 50%.
In addition, when making two-sided laminate for wiring board with metal forming, by on the polyimide resin layer of the single face laminate for wiring board that adopts said method to obtain directly or formed and behind the adhesive linkage metal forming is added thermo-compressed and obtain.Hot pressing temperature when adding thermo-compressed for this is not particularly limited, and is preferably more than the glass transition temperature that equals employed polyimide resin.In addition, for hot pressing pressure, because of the kind of employed pressue device is different, but preferred 1～500kg/cm
2Scope.In addition, the preferred metal forming that use this moment can be used the metal forming identical with above-mentioned metal forming, and its preferred thickness also is smaller or equal to 50 μ m, the more preferably scope of 5～40 μ m.
Constitute the polyimide resin layer of laminate for wiring board of the present invention, can be by the aromatic diamine shown in the general formula (2), characteristic is controlled with the various combinations of other aromatic diamines of itself and usefulness and aromatic tetracarboxylic acid or its acid dianhydride.Preferred polyimide resin layer is a coefficient of linear expansion smaller or equal to the storage modulus under 30ppm/ ℃, 23 ℃ smaller or equal to 6GPa and the hydroscopicity polyimide resin layer smaller or equal to 0.8wt%, from stable on heating viewpoint, glass transition temperature should be more than or equal to 350 ℃, and the minimizing temperature of 5% weight in the thermogravimetric analysis (Td 5%) should be in 500～600 ℃ scope, in addition, humidity expansion coefficient all should be smaller or equal to 10ppm/%RH in TD, MD direction.Should illustrate that 5% weight reduces temperature and is also referred to as heat decomposition temperature.
Embodiment
Below, specifically describe content of the present invention according to embodiment, but the invention is not restricted to the scope of these embodiment.
The dummy suffix notation that uses among the embodiment etc. is expressed as follows.
PMDA: pyromellitic acid anhydride
BPDA:3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride
M-MOB:2,2 '-dimethoxy benzidine
M-EOB:2,2 '-diethoxy benzidine
M-POB:2,2 '-two positive propoxy benzidine
M-PHOB:2,2 '-two phenoxy group benzidine
DAPE:4,4 '-diamino-diphenyl ether
M-TB:2,2 '-dimethylbenzidine
TPE-R:1, two (4-amino-benzene oxygen) benzene of 3-
BAPP:2, two (the 4-amino-benzene oxygen phenyl) propane of 2-
DMAc:N, the N-dimethylacetylamide
In addition, be shown in the assay method of the various rerum naturas among the embodiment and condition following.
[glass transition temperature (Tg), storage modulus (E ')]
With dynamic thermal machinery analyses (DMA) device to the polyimide film that makes among each embodiment (10mm * 22.6mm) measures with 5 ℃ of/minute dynamic viscoelastics when 20 ℃ are warmed up to 500 ℃, obtain glass transition temperature (tan δ maximum) and 23 ℃, 100 ℃ storage modulus (E '
23And E '
100).
[mensuration of coefficient of linear expansion (CTE)]
With thermo-mechanical analysis (TMA) device limit the load limit that the polyimide film of 3mm * 15mm size applies 5.0g is carried out tension test with certain programming rate 30 ℃～260 ℃ temperature range.Obtain coefficient of linear expansion by polyimide film with respect to the elongation of temperature.
[mensuration of heat decomposition temperature (Td5%)]
Use thermogravimetric analysis (TG) device to measure to the polyimide film of 10～20mg, obtain 5% weight and reduce temperature (Td5%) with the weight change of certain speed when 30 ℃ are warmed up to 550 ℃.
[mensuration of hydroscopicity (RMA)]
The polyimide film (each 3) of 4cm * 20cm after under 120 ℃ dry 2 hours, is left standstill in the thermostatic constant wet chamber of 23 ℃/50%RH more than or equal to 24 hours, obtain by following formula by the weight change before and after it.
RMA (%)=[(weight after the moisture absorption-drying back weight)/dry back weight] * 100
[mensuration of humidity expansion coefficient (CHE)]
On the Copper Foil of polyimides/copper foil laminated body of 35cm * 35cm, the etching resist layer is set, it is formed on the pattern of ordering at 12 places configuration diameter 1mm at interval with 10cm for foursquare four limits of 30cm on one side.Copper Foil exposed portions serve to etching resist aperture portion is carried out etching, makes the CHE mensuration polyimide film with Copper Foil remanent point, 12 place.This film at 120 ℃ down after dry 2 hours, is left standstill in the constant temperature and humidity machine of 23 ℃/50%RH more than or equal to 24 hours, with the change in size between two-dimentional gauging machine mensuration Copper Foil point (0～50%RH), obtain humidity expansion coefficient.
Embodiment
Synthesis example 1～18
The polyamic acid that uses in synthetic embodiment and the comparative example.
Under nitrogen current, the diamines shown in the table 1 is dissolved among the 43g solvent DMAc.Then, add the tetracarboxylic dianhydride shown in the table 1.Then, at room temperature the solution continuous stirring was carried out polymerization reaction in 3～4 hours, make Huang～umbrinaceous viscous solution as 18 kinds of polyamic acids (PA) A～R of polyimide precursor.Reduced viscosity (the η of each polyamic acid solution
Sp/ C) be in 3～6 the scope.In addition, weight average molecular weight Mw is shown in table 1.
Table 1
| Synthesis example | Diamines (g) | PMDA (g) | BPDA (g) | PA | η sp/C (dl/g) | Mw ×10 3 | |
| 1 | m-MOB 3.45 | 3.08 | A | 5.7 | 263 | ||
| 2 | m-MOB 3.88 | 2.73 | 0.92 | B | 5.3 | 259 | |
| 3 | m-MOB 3.07 | 3.45 | C | 4.9 | 225 | ||
| 4 | m-EOB 3.62 | 2.90 | D | 4.5 | 150 | ||
| 5 | m-EOB 3.54 | 2.27 | 0.71 | E | 4.1 | 474 | |
| 6 | m-EOB 3.25 | 3.27 | F | 3.4 | 58 | ||
| 7 | m-POB 3.78 | 2.74 | G | 5.8 | 112 | ||
| 8 | m-POB 3.70 | 2.15 | 0.68 | H | 5.2 | 58 | |
| 9 | m-POB 3.41 | 3.11 | I | 4.6 | 160 | ||
| 10 | DAPE 2.39 | 2.61 | J | 150 | |||
| 11 | m-PHOB 4.10 | 2.43 | K | 218 | |||
| 12 | m-PHOB 3.99 | 1.89 | 0.64 | L | 208 | ||
| 13 | m-EOB 1.96 | DAPE 1.45 | 3.11 | M | 120 | ||
| 14 | m-POB 2.67 | TPE-R 1.12 | 2.74 | N | 188 | ||
| 15 | m-MOB 3.44 | TPE-R 0.46 | 2.69 | 0.91 | O | 220 | |
| 16 | m-PHOB 2.17 | m-TB 0.43 TPE-R 0.60 | 4.38 | P | 215 | ||
| 17 | m-POB 2.36 | m-TB 1.36 | 2.80 | Q | 229 | ||
| 18 | BAPP 5.00 | 2.50 | 0.18 | R | 325 | ||
Embodiment 1
Before the solution of polyamic acid (PA) A～R that in coating synthesis example 1～18, makes, add DMAc viscosity adjustment is moored to about 250.Then, using spreader to be applied to respectively on the Copper Foil of thick 35 μ m makes dried thickness be about 15 μ m, after under 50～130 ℃ dry 2～60 minutes, under 130 ℃, 160 ℃, 200 ℃, 230 ℃, 280 ℃, 320 ℃, 360 ℃, respectively carry out 2～30 minutes interim heat treatment again, on Copper Foil, form polyimide layer, obtain 18 kinds of laminates.The laminate that will be made by the solution of the polyamic acid A that obtains in the synthesis example 1 is designated as laminate A, below identical.The laminate J that the solution that uses the polyamic acid J that obtains in the synthesis example 10 is made as a comparative example.In addition, the laminate R that uses the solution of the polyamic acid R that obtains in the synthesis example 18 to make is used to estimate 1 layer the characteristic of polyimide layer of laminate M1～M3 of aftermentioned embodiment.
Laminate A～R for embodiment 1, use ferric chloride in aqueous solution that the Copper Foil etching is removed, make 18 kinds of polyimide films, measure glass transition temperature (Tg), storage modulus (E '), thermal coefficient of expansion (CTE), 5% weight reduces temperature (Td5%), hydroscopicity (RMA) and humidity expansion coefficient (CHE).
Each measurement result is shown in table 2.
Table 2
| Run No. | Laminate | Tg (℃) | E’ 23 (GPa) | E’ 100 (GPa) | CTE (ppm/ ℃) | Td5％ (℃) | RMA (wt％) | CHE (ppm/％RH) | |
| TD | MD | ||||||||
| 1 | A | 403 | 10.79 | 10.47 | -3.6 | 457 | -- | -- | -- |
| 2 | B | 365 | 10.30 | 9.26 | -0.9 | 481 | 1.69 | 9.8 | 9.7 |
| 3 | C | 430 | 10.20 | 9.12 | 8.7 | 477 | 1.35 | 9.7 | 7.6 |
| 4 | D | 378 | 9.51 | 8.08 | -7.7 | 431 | 1.31 | 0.3 | 0.3 |
| 5 | E | 378 | 6.80 | 5.36 | 14 | 434 | 1.27 | 5.4 | 5.5 |
| 6 | F | 270 | 5.40 | 4.48 | 58 | 443 | 0.88 | 9.4 | 8.8 |
| 7 | G | 378 | 4.90 | 3.91 | -11 | 426 | 0.64 | -2.2 | -0.5 |
| 8 | H | 365 | 4.49 | 3.95 | 24 | 439 | 0.83 | -1.0 | 0 |
| 9 | I | 276 | 3.80 | 2.82 | 66 | 421 | 0.76 | -7.9 | -7.2 |
| 10 | J | 387 | 2.48 | 2.22 | 41 | ＞505 | 1.70 | 34 | 36 |
| 11 | K | 394 | 5.17 | 4.50 | 17 | 539 | 0.55 | -2.1 | -1.6 |
| 12 | L | 391 | 4.95 | 4.35 | 51 | 543 | 0.68 | -4.1 | -4.2 |
| 13 | M | 376 | 4.6 | 3.66 | 21 | 465 | 1.37 | 9.7 | 9.9 |
| 14 | N | 371 | 5.6 | -- | 17 | 437 | 0.55 | -1.2 | -1.8 |
| 15 | O | 360 | 9.1 | -- | 7.1 | 482 | 1.43 | 6.9 | 7.5 |
| 16 | P | 370 | 4.5 | -- | 15.1 | 528 | 0.69 | * | * |
| 17 | Q | 374 | 8.7 | -- | 12.0 | 490 | 1.03 | 3.1 | 2.7 |
| 18 | R | 311 | 3.1 | -- | 56.1 | 490 | 0.64 | -- | -- |
Embodiment 2
The solution of the polyamic acid R of modulation in the synthesis example 18 is uniformly applied on the thick Copper Foil of 18 μ m with the thickness of 25 μ m, desolvates to remove at 130 ℃ of following heat dryings then.Then, it is stacked to carry out evenly to be coated with the solution of the polyamic acid E of modulation in the synthesis example 5 with the thickness of 195 μ m thereon, desolvates to remove at 70 ℃～130 ℃ following heat dryings.On polyamic acid E layer, evenly be coated with the solution of the polyamic acid R of modulation in the synthesis example 18 again, desolvate to remove at 135 ℃ of following heat dryings with the thickness of 37 μ m.Then, heat-treat and make its imidizate, obtain on Copper Foil, having formed the laminate M1 of the insulating resin layer of the about 25 μ m of gross thickness that constitute by 3 strata acid imide resin beds thereby be elevated to 360 ℃ from room temperature with about 5 hours.The dried thickness of polyamic acid resin layer that is coated with on Copper Foil is the about 3.5 μ m of the about 19 μ m/ of about 2.5 μ m/ with the order of R/E/R.
Embodiment 3～4
Similarly to Example 2, obtain on Copper Foil, having formed the laminate M2 and the M3 of the insulating resin layer of the about 25 μ m of total bed thickness that constitute by 3 strata acid imide resin beds.The kind of the polyamic acid solution that is coated with on Copper Foil and dry back thickness are successively: M2 is the about 3.5 μ m of the about 19 μ m/R of the about 2.5 μ m/O of R, and M3 is the about 3.5 μ m of the about 19 μ m/R of the about 2.5 μ m/Q of R.
For the laminate M1～M3 that obtains among the embodiment 2～4, measure cementability intensity.In addition, use ferric chloride in aqueous solution that the Copper Foil etching is removed, make polyimide film, measure the thermal coefficient of expansion (CTE) in the 3 strata imide layer.
Each measurement result is shown in table 3.
Table 3
| Embodiment | Laminate | Layer structure | Cementability (kN/m) | CTE (ppm/℃) |
| 2 | M1 | R/E/R | 1.4 | 17 |
| 3 | M2 | R/O/R | 1.5 | 16 |
| 4 | M3 | R/Q/R | 1.4 | 20 |
Laminate for wiring board of the present invention, the excellent heat resistance as the polyimide resin layer of insulating barrier has agent of low hygroscopicity, and dimensional stability is also excellent, without all problems from adhesive linkage, also has the effect that suppresses the warpage that humidity produces.In addition, therefore the polyimide resin layer of insulating barrier has no anisotropic feature in face because the difference of the humidity expansion coefficient of TD direction and MD direction is little, can be widely used in the parts of field of electronic materials.Be specially adapted to FPC, HDD draft hitch with purposes such as substrates.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004051167 | 2004-02-26 | ||
| JP051167/2004 | 2004-02-26 |
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| CNB200580005515XA Expired - Fee Related CN100566503C (en) | 2004-02-26 | 2005-02-21 | Laminate for wiring board |
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|---|---|
| JP (1) | JP4768606B2 (en) |
| KR (1) | KR101077405B1 (en) |
| CN (1) | CN100566503C (en) |
| TW (1) | TW200528490A (en) |
| WO (1) | WO2005084088A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312329A (en) * | 2016-04-27 | 2017-11-03 | 新日铁住金化学株式会社 | Polyimide film and copper-clad laminated board |
| CN109575596A (en) * | 2017-09-29 | 2019-04-05 | 日铁化学材料株式会社 | Polyimide film and metal-clad stack |
| CN109575831A (en) * | 2018-11-20 | 2019-04-05 | 深圳市弘海电子材料技术有限公司 | Low bounce-back power cover film and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4907142B2 (en) * | 2005-10-13 | 2012-03-28 | 新日鐵化学株式会社 | Aromatic polyamic acid, polyimide and laminate for wiring board |
| JP4962056B2 (en) * | 2007-03-09 | 2012-06-27 | 東洋紡績株式会社 | Copper-clad laminated film and method for producing the same |
| WO2008126559A1 (en) * | 2007-03-30 | 2008-10-23 | Nippon Steel Chemical Co., Ltd. | Polyimide film |
| CN110241389A (en) * | 2018-03-08 | 2019-09-17 | 日铁化学材料株式会社 | Vapor deposition mask, polyamic acid for vapor deposition mask formation, laminate for vapor deposition mask formation, and manufacturing method of vapor deposition mask |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60250031A (en) * | 1984-05-28 | 1985-12-10 | Hitachi Ltd | Low-thermal expansion resin material |
| JPH06234916A (en) * | 1993-02-09 | 1994-08-23 | Central Glass Co Ltd | Low-stress polyimide composition and precursor composition solution |
| WO1998008216A1 (en) * | 1996-08-19 | 1998-02-26 | Nippon Steel Chemical Co., Ltd. | Laminate for hdd suspension and its manufacture |
| JP3794446B2 (en) * | 1997-08-05 | 2006-07-05 | 株式会社カネカ | Polyimide film for hard disk suspension wiring substrate |
| JP3704920B2 (en) * | 1997-11-21 | 2005-10-12 | 宇部興産株式会社 | Manufacturing method of magnetic head suspension |
| JP3486357B2 (en) * | 1998-12-28 | 2004-01-13 | 日本電信電話株式会社 | Optical polyimide substrate |
| JP2002338710A (en) * | 2001-03-16 | 2002-11-27 | Sumitomo Bakelite Co Ltd | Plastic base plate for indication element |
-
2005
- 2005-02-21 JP JP2006510413A patent/JP4768606B2/en not_active Expired - Fee Related
- 2005-02-21 CN CNB200580005515XA patent/CN100566503C/en not_active Expired - Fee Related
- 2005-02-21 KR KR1020067017525A patent/KR101077405B1/en active IP Right Grant
- 2005-02-21 WO PCT/JP2005/002729 patent/WO2005084088A1/en active Application Filing
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312329A (en) * | 2016-04-27 | 2017-11-03 | 新日铁住金化学株式会社 | Polyimide film and copper-clad laminated board |
| CN109575596A (en) * | 2017-09-29 | 2019-04-05 | 日铁化学材料株式会社 | Polyimide film and metal-clad stack |
| CN109575596B (en) * | 2017-09-29 | 2022-08-23 | 日铁化学材料株式会社 | Metal-clad laminate |
| CN109575831A (en) * | 2018-11-20 | 2019-04-05 | 深圳市弘海电子材料技术有限公司 | Low bounce-back power cover film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005084088A1 (en) | 2005-09-09 |
| TWI372156B (en) | 2012-09-11 |
| TW200528490A (en) | 2005-09-01 |
| KR20070007296A (en) | 2007-01-15 |
| JPWO2005084088A1 (en) | 2008-01-17 |
| JP4768606B2 (en) | 2011-09-07 |
| CN100566503C (en) | 2009-12-02 |
| KR101077405B1 (en) | 2011-10-26 |
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