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.