CN1239622C - Polyimide resin precursor solution, laminates for electronic components made by using the solution and process for production of the laminates - Google Patents
Polyimide resin precursor solution, laminates for electronic components made by using the solution and process for production of the laminates Download PDFInfo
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- CN1239622C CN1239622C CNB018222412A CN01822241A CN1239622C CN 1239622 C CN1239622 C CN 1239622C CN B018222412 A CNB018222412 A CN B018222412A CN 01822241 A CN01822241 A CN 01822241A CN 1239622 C CN1239622 C CN 1239622C
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
Abstract
Laminates for electronic components are produced by applying a polyimide resin precursor solution containing a palladium compound on a polyimide substrate, drying the resulting coating to form a polyimide resin precursor layer, irradiating this layer with ultraviolet rays in the presence of a hydrogen donor to form nuclei for primer plating, forming a metal primer layer by electroless plating, and converting the polyimide resin precursor layer into a polyimide resin layer through imidation by heating either after or before the formation of a surface plating layer. The invention provides laminates for electronic components which are extremely improved in adhesion to metal layers without impairing the characteristics inherent in the substrate and are excellent in insulating properties, and polyimide resin precursor resin solution to be used in the production of the laminates.
Description
Technical field
What the present invention relates to is, has the manufacture method of the electronic unit material base material that the microfabrication of polyimide resin layer uses.
Background technology
Adopt the polyimide base material that covers copper as flexible printed board, TAB material and CSP material, but, follow the miniaturization of machine and the high speed of signal reception and registration speed etc., the microfabrication of then essential fine distribution of high-density and fine path etc., and more and more require the high material of adhesion strength of metallic membrane.
In the past, in order to obtain the high copper-clad polyimide base material of adhesion strength, the method that adopts is, after polyimide surface is carried out dry type pre-treatments such as ion bombardment and corona discharge, adhere to underlying metals such as nickel and chromium with sputtering method, carry out electroless plating more thereon and cover (electroless plating) and electrolytic coating formation metallic membrane.
Yet, in the method, need expensive machine in order under vacuum, to carry out pre-treatment and sputter, the result descends production, cost improves, thus industrial hard to say be advantageous method.
On the other hand, do not carry out pre-treatment or sputter process, give catalyzer and electroless plating covers or electrolytic coating is made the occasion of copper-clad polyimide, though need not expensive machine but adopt, but the adhesion strength between metal and the polyimide is low, so there is out of use problem in practicality.
As the measure that forms metal level at substrate surface, it is the method for the palladium chloride catalyst of reductive agent with the tin protochloride that employing is arranged, recently, for on glass or ceramic surface, forming metal level, at electronic mounting technology (the real packing technique of エ レ Network ト ロ ニ Network ス) (VOL.11, No.6, P 32,1995) method of report is in, by Zinc oxide film and Palladous chloride reaction absorption palladium catalyst, again with reductive agent reductive method or the photosemiconductor characteristic of utilizing zinc oxide to the zinc oxide irradiates light, reducing metal ionic method, but present method is only limited to zinc-oxide film can be formed easily, and inorganic materials such as glass that tackiness is high and pottery, then inapplicable to organic materials.
(the 13rd the lecture collection P183 of electronic mounting association of report in addition, 1999) be, basic hydrolysis is carried out on the surface of Kapton, make after the polyamic acid, make it to adsorb after copper sulfate or the Palladous chloride, with the ultraviolet method of sodium formiate as reductive agent irradiation Cooper-Hewitt lamp.But, form length very of needed time of catalyst core by uviolizing, and become alkalescence owing to reductive agent decomposes generation NaOH, the problem of Kapton generation deterioration and so on is then arranged.
Also have, above-mentioned method all is only to form the method for metal level on substrate surface, enters into so-called grappling (anchor) effect among the base material so can not obtain metal level.
Therefore, propose, on the surface of plated body, form after the filming of salt of dissolving precious metal, with hydrogen, CO, H for addressing the above problem once
2Reducing gas such as S carry out reductive method (special fair 5-61296 number) and will be with reductive agent directly reductive metallic compound and method (spy opens flat 5-306469 number) that can the combination of contact reductive metallic compound.
Yet, the method for record in special fair 5-61296 number, the blast of reducing gas and toxicity etc. are a lot of in the problem of secure context.And the special method of opening record in flat 5-306469 number, because the addition of metallic compound must reach per 100 parts by weight resin and be about 200 weight parts, the result has lost the characteristic (intensity, insulativity etc.) of resin, perhaps metallic compound does not remain in the resin with being reduced fully, causes insulativity problems such as metal ion transport sometimes easily.
The objective of the invention is to, provide and do not use expensive machine, very high and base material is not lost original characteristic, electronic component-use base material that insulativity is high with the adhesion strength of metal, with the inexpensive method of manufacturing of electronic component-use base material, and the polyimide resin precursor solution that is used to make the electronic component-use base material.
The content of invention
Polyimide resin precursor solution among the present invention is characterized in that palladium compound is evenly dispersed in the polyimide resin precursor, and palladium compound and polyimide resin precursor formation coordination compound.
And, preferably, as polyimide resin precursor, use is by at least a polyimide resin precursor varnish (varnish) that constitutes of the derivative of polyamic acid, polyamic acid, as palladium compound, use palladium methyl ethyl diketone coordination compound or organic acid palladium salt to form the polyimide resin precursor layer of homogeneous.
In addition, electronic component-use base material among the present invention, it is characterized in that, on polyimide base material, form in the electronic component-use base material of overlay coating between polyimide base material and overlay coating, to have the polyimide resin layer that uses polyimide resin precursor solution to form.
In addition, the manufacture method of the electronic component-use base material among the present invention, it is characterized in that the polyimide resin precursor solution that will contain palladium compound on polyimide base material applies the dry polyimide resin precursor layer that forms, then hydrogen donor (alms giver; Donor) existing down, irradiation ultraviolet radiation forms after the clad substate nuclear, cover by electroless plating and handle to form the clad substate metal level, further after forming overlay coating or make above-mentioned polyimide resin precursor layer add hot-imide before the formation to make polyimide resin layer.
And, as the hydrogen donor, when adopting water, alcohol or alcohol solution, the palladium ion of the palladium coordination compound that causes owing to uviolizing efficiently and stably can be reduced into palladium metal, so be preferred.
The simple declaration of accompanying drawing
Fig. 1 is the sectional drawing of electronic component-use base material of the present invention.
Fig. 2 is the manufacture method figure that electronic component-use base material of the present invention is shown in the section mode by sequence of process steps.Wherein, (a) be to be illustrated in the sectional drawing that forms the state of polyimide resin precursor layer on the polyimide base material, (b) be to be illustrated in the hydrogen donor to have the sectional drawing of the state of irradiation ultraviolet radiation formation clad substate nuclear down, (c) be to illustrate by electroless plating to cover the sectional drawing of handling the state that forms the clad substate metal level, (d) being the sectional drawing that the state that forms overlay coating is shown, is to illustrate to make the polyimide resin precursor layer add the sectional drawing that hot-imide makes the state of polyimide resin layer (e).
Fig. 3 is illustrated in the polyimide resin precursor solution that viscosity when adding palladium methyl ethyl diketone coordination compound changes and the viscosity variation diagram of polyimide resin precursor solution.
Fig. 4 illustrates XPS analysis that the bond energy of the palladium of showing the polyimide resin precursor film before and after the uviolizing changes figure as a result.
Fig. 5 is the auger analysis record diagram of the depth direction of nickel-plated substrate metal level behind the non-electrolytic ni plating and polyimide resin precursor film.
The preferred plan that carries out an invention
Electronic component-use base material 1 in embodiment of the present invention, its structure as shown in Figure 1, the part of the clad substate metal level 6 that exists between polyimide base material 2 and overlay coating 7 is used polyimide resin precursor solution new polyimide resin layer that forms on polyimide base material 2 and wraps.
The manufacture method of the electronic component-use base material in this embodiment, as shown in Figure 2, be to apply dry polyimide resin precursor layer 3 (Fig. 2 (a)) that form by the polyimide resin precursor solution that on polyimide base material 2, will contain palladium compound 4, follow irradiation ultraviolet radiation 9 in the presence of hydrogen donor 8, make the palladium ion in the palladium compound 4 be reduced into palladium metal, form clad substate nuclear 5 (Fig. 2 (b)) thus, cover processing by electroless plating and form clad substate metal level 6 (Fig. 2 (c)), and then formation overlay coating 7 (Fig. 2 (d)), then, above-mentioned polyimide resin precursor layer is added hot-imide, make polyimide resin layer (Fig. 2 (e)), make the method for electronic component-use base material 1.
Measure the metal level of the electronic component-use base material (copper electroplating thickness 24 μ m) so obtain and the result of the adhesion strength between polyimide resin layer is by JISC-6481, stripping strength be 11～14N/cm (1100～1400gf/cm), be equal to or greater than in the past with sputter/electroless plating and cover/stripping strength of the electronic component-use base material that process for electrolytic coating is made.
As the polyimide base material that uses among the present invention, the non-thermal plasticity polyimide resin is arranged, thermoplastic polyimide resin, for example, can enumerate, the polyimide that commercially available pyromellitic acid acid anhydride (PMDA) and oxo pentanoic (ODA) constitute, the polyimide that biphenyltetracarboxyacid acid acid anhydride (BTDA) and Ursol D (PDA) constitute, with these monomeric multipolymers, have in aromatic tetracarboxylic acid's acid anhydride and the molecule-O-,-CO-, the thermoplastic polyimide that the aromatic diamine of folding base such as-Si-(く っ I ょ く I) etc. constitute, also have with the solvable type thermoplastic polyimide of solvent of the multipolymer of ester ring type carboxylic acid anhydride etc. etc., these polyimide base materials use mainly as the film like base material in electronic unit material field.
As polyimide resin precursor, employing be that the polyamide acid varnish by the monomer component identical with polyimide resin obtains perhaps contains the polyamide acid varnish of photosensitivity group etc. in molecule.For example, can enumerate, " the U-ワ ニ ス " of " the ト レ ニ-ス " varnish in east beautiful (strain) and " Off オ ト ニ-ス " varnish, the emerging product of space portion (strain) etc. can mix use with polyimide resin precursor varnish and the solvable type polyimide varnish of solvent.
The thermoplastic polyimide varnish " SPI-200N " of Nippon Steel's chemistry system etc. is arranged as the solvable type polyimide varnish of solvent.
As palladium compound, various salt or organic carbonyl coordination compound of palladium arranged, can enumerate hydrochloride, vitriol, acetate, oxalate, Citrate trianion etc. as palladium salt.In addition, as organic carbonyl compound, can enumerate β-esters of keto-carboxylic acids such as beta-diketon classes such as methyl ethyl diketone and diphenylpropane-1,3-dione(DPPO) and methyl aceto acetate etc.Particularly, the organic salt or the coordination compound of palladium acetate and methyl ethyl diketone coordination compound etc., because obtain easily, to the solvability and the thermostability of organic solvent, after photoresponse, do not have mineral ion such as chlorion residual etc. in the resin, so be preferred the use.
Above-mentioned organic carbonyl coordination compound is dissolved into as the N-methyl 2-Pyrrolidone of the solvent of polyimide resin precursor (n-メ チ Le 2-PVC ロ リ ジ ノ Application) (NMP) or after in NN '-N,N-DIMETHYLACETAMIDE (DMAc), mixed dissolution equably in polyimide resin precursor varnish, for example, use rotation coating machine or rod to be coated with machine, also have silk screen printing etc., be coated on the polyimide base material with thin film layer, below the heat decomposition temperature of organic carbonyl coordination compound, under the temperature below 150 ℃, carry out drying usually.
The thickness of dried polyimide resin precursor layer is generally 0.1-10 μ m, ligand compound substrate concentration in the polyimide resin precursor layer in addition, according to the ligand compound species and different, for example, preferably, field boundary at palladium methyl ethyl diketone coordination compound or acid chloride is combined into about 0.1～10 weight %, is combined into about 1～5 weight % at the field boundary of Palladous chloride.
Silk screen print method without operations such as photoetching directly on polyimide base material, form distribution and connection bump (bump) thus etc. be preferred.
Form the situation of polymer complex compound by polyimide resin precursor and palladium compound reaction, that puts down in writing among the embodiment 12～14 as described later is such, and the viscosity during from interpolation palladium compound polyimide resin precursor rises and gel formation can be recognized.
As described later among the embodiment 12 record like that, figure 3 illustrates that viscosity when adding palladium methyl ethyl diketone coordination compound in polyimide resin precursor solution changes and the viscosity variation of polyimide resin precursor solution.
Also can see same tendency when in addition, adding acid chloride or Palladous chloride replacement palladium methyl ethyl diketone coordination compound.But that puts down in writing in the comparative example 8 as described later is such, and when adding acetylacetone copper (II) coordination compound replacement palladium methyl ethyl diketone coordination compound, the viscosity that solution does not take place fully changes and gel phenomenon.
Therefore, the formation of reacting the polymer complex compound that causes by polyimide resin precursor and palladium compound is that palladium ion is peculiar, the functional group reactions of palladium ion and polyimide resin precursor, be formed on palladium ion coordination in the polymer molecule coordination compound, and think to be in the state that participates in as a composition.
Promptly, think in the dry polyimide resin precursor layer that forms of polyimide base material surface-coated, be not only only uniform distribution of palladium ion, and a composition of the polymer molecule that exists as the polyimide resin precursor laminar surface is distributing also to expose like that on the surface.
In fact, that puts down in writing among the embodiment 1 as described later is such, from the result that the XPS measurement result and the auger spectrum shown in Fig. 5 of the polyimide resin precursor laminar surface shown in Fig. 4 are measured, can confirm that these palladium coordination compoundes also exist equably on polyimide resin layer surface and resin layer depth direction.
As the ultraviolet ray of using among the present invention, can adopt from the ultraviolet ray below the wavelength 450nm of mercury UV-lamp or the radiation of ultraviolet laser generating unit, the following ultraviolet ray of 370nm is that effectively the ultraviolet ray of 254nm is effective especially.As UV-lamp, can preferably use commercially available Cooper-Hewitt lamp.
Can see that from the XPS measurement result of the polyimide resin precursor laminar surface that is shown in Fig. 4 palladium ion is reduced into palladium metal.
That is, palladium polymer complex compound absorb light during irradiation ultraviolet radiation and being excited excites the palladium ion in the coordination compound molecule to revert to palladium metal and form substrate plating nuclear in the presence of the hydrogen donor.
In addition, in order to promote the photoresponse of coordination compound,, can also add sensitizer as long as the tackiness of metal and polyimide etc. is not had special bad influence.
As the hydrogen donor, water, alcohol are arranged, also have alcohol solution etc., but especially preferably use, not too have in above-mentioned ultraviolet wavelength zone ultraviolet radiation absorption and have the alcohol solution of appropriate wetting quality with the polyimide resin precursor laminar surface.In addition, metal ion is reduced into the reaction of metal, overslaugh reaction during aerobic is so preferably cut off air (oxygen) when uviolizing.Normally under the state that polyimide base material is immersed in the hydrogen donor, shine, but at the hydrogen donor is that the field boundary of water closes, can adopt in the water one side such as irradiation to supply with moisture from the outside and shine on one side, it is possible moisture fully being adsorbed onto in the polyimide resin precursor layer and utilizing.
In addition, the ultraviolet irradiation time is according to ultraviolet irradiation intensity and different, but when the uviolizing of adopting from UV-lamp, common irradiation time is about 1 minute～20 minutes, and close at the field boundary of employing from the uviolizing of generating device of laser, common irradiation time is in 60 seconds.As ultraviolet irradiating dose, when the ultraviolet luxmeter UV-02 that makes manufacturing of オ-Network measures, be 500～15000mJ/cm
2About, preferred especially 1500～9000mJ/cm
2About.When irradiation dose is too much, also can cause polymkeric substance self-inflicted injury etc., so be not preferred.
Polyimide base material with polyimide resin precursor layer of uviolizing, carrying out electroless plating with clad substate nuclear as catalyzer covers to handle and forms after the clad substate metal level, adopt processing of electroless plating copper and copper electroplating processing etc., metal deposition is proceeded to the thickness of metal film that reaches necessary, again behind the washing and drying, in nitrogen atmosphere, be heated to 400 ℃, carry out imidization.Moreover, add hot-imide if after the substrate metal layer that is covered processing by electroless plating forms, just can carry out in any stage before and after electrolytic coating.
As bathing for the electroless plating that forms substrate metal layer, there is no particular limitation, but, preferably use from neutrality to weakly acidic Hypophosporous Acid, 50 salt or the nickel plating bath of dimethylamino borane class usually from the shielding of metal ion and the resistance to chemical reagents of polyimide resin precursor (alkali resistance) are considered.In addition, can use common copper electroplating and electrolytic ni plating bath etc. for the electrolysis plating bath.
Use the electronic component-use base material (copper electroplating thickness 18 μ m) that obtains as stated above, make the distribution of L/S=100/100 (μ m) by photo-engraving process, after again distribution being removed with the polyimide resin precursor layer employing etching method of outside part, as can be known, obtained 1.5 * 10 when pressing JISC-5016 mensuration wire insulation resistance
12This high insulation resistance of Ω cm.
The electronic component-use base material that obtains by the present invention is because clad substate nuclear is present in the polyimide resin, so it is very high to make plating be coated with the adhesion strength of substrate metal layer and polyimide resin by its anchoring effect.In addition, insulativity is also excellent between the line after distribution forms, and the electronic unit material of using as microfabrication can fully use.
Below, specifically describe the present invention by embodiment and comparative example.
The solution that will dissolve commercially available palladium methyl ethyl diketone coordination compound (below abbreviation make the palladium coordination compound) in N-methyl 2-Pyrrolidone (hereinafter to be referred as making NMP) adds among polyimide resin precursor varnish " the ト レ ニ-ス " #3000 of Dong Li company (strain), regulates varnish solution and makes the palladium coordination compound content of average varnish solution become 1wt/vol%.This varnish solution contains the palladium coordination compound that average polyimide resin precursor is roughly 5wt/vol%.
Moreover so-called 1wt/vol% refers to, and for example, palladium coordination compound 0.01g is dissolved in the concentration in 1ml " ト レ ニ-ス " the varnish solution.
Then, handle the test piece 10 * 10cm (thickness 50 μ m) of the polyimide base material " ユ-ピ レ Star Network ス-S " of the emerging product of space portion (strain) with the 1%NaOH aqueous solution and the 1%HCl aqueous solution, with pure water clean, after the drying, adopt rod to be coated with machine and apply above-mentioned varnish solution, in room temperature and 120 ℃ of following dryings, obtain the base material of the about 5 μ m of coating thickness.The result that substrate surface is carried out XPS analysis has confirmed the existence of palladium ion from the teeth outwards as shown in Figure 4.
Water droplet to above-mentioned base material, sandwiching under the state that forms moisture film between the quartz plate, is used Cooper-Hewitt lamp irradiation ultraviolet radiation 3 minutes.The result that ultraviolet irradiating dose is measured at the luxmeter " UV-02 " of making manufacturing of オ-Network is 4500mJ/cm
2The result that substrate surface is carried out XPS analysis detects metallic palladium as shown in Figure 4, distinguishes that palladium ion is reduced into metallic palladium.
Then, with shone ultraviolet base material put into be warmed to 65 ℃, bathe " エ Application プ レ-ト Ni-426 " (pH=6～7) when flooding 5 minutes with the sodium hypophosphite of メ Le テ Star Network (strain) as the electroless plating nickel of reductive agent, obtain having formed base material with even metal glossy coating in uviolizing portion.With above-mentioned base material washing, drying, form the clad substate layer.Measure the nickel plating portion of gained base material and polyimide resin precursor layer auger spectrum the result as shown in Figure 5, detection shows that nickel reaches the further portion of polyimide resin precursor layer.
Further, carry out current density 3.3A/dm with the electrolysis copper plating solution
2Electrolytic coating, obtain the copper lining polyimide base material of the thick 24 μ m of copper film.
In nitrogen atmosphere, after 150 ℃ of following dryings, reheat to 400 ℃ kept 15 minutes at 400 ℃ with above-mentioned base material, make polyimide resin precursor layer imidization after, be cooled to 20 ℃.
Measuring the metal part of gained base material and the result of the stripping strength between polyimide resin layer with the method for stipulating among the JISC-6481, is 14N/cm (1400gf/cm).
Embodiment 2
The palladium coordination compound content of the polyimide resin precursor liquid of embodiment 1 is altered to 0.5wt/vol%, carries out same processing, make the electronic component-use base material of the thick 22 μ m of copper film.Measuring the metal part of gained base material and the result of the stripping strength between polyimide resin layer with the method for stipulating among the JISC-6481, is 12N/cm (1200gf/cm).
Embodiment 3
The ultraviolet irradiating dose of embodiment 1 is changed to 7500mJ/cm
2, carry out same processing.
Embodiment 4
The ultraviolet irradiating dose of embodiment 1 is changed to 9000mJ/cm
2, carry out same processing.
Embodiment 5
The palladium coordination compound content of the polyimide resin precursor liquid of embodiment 1 is altered to 0.5wt/vol%, ultraviolet irradiating dose is changed to 7500mJ/cm
2, carry out same processing.
Embodiment 6
The content of the palladium coordination compound of the polyimide resin precursor liquid of embodiment 1 is altered to 0.5wt/vol%, ultraviolet irradiating dose is changed to 9000mJ/cm
2, carry out same processing.
Thick and stripping strength is shown in Table 1 from the copper film of embodiment 1 to embodiment 6.
Table 1
| Embodiment No. | Palladium coordination compound content wt/vol% | Ultraviolet irradiating dose mJ/cm 2 | The thick μ m of copper film | Stripping strength N/ |
| 1 | 1.0 | 4500 | 24 | 14 |
| 2 | 0.5 | 4500 | 22 | 12 |
| 3 | 1.0 | 7500 | 24 | 14 |
| 4 | 1.0 | 9000 | 24 | 13.5 |
| 5 | 0.5 | 7500 | 20 | 11 |
| 6 | 0.5 | 9000 | 20 | 11.5 |
Embodiment 7
To dissolve the solution of commercially available acid chloride among the NMP, added among polyimide resin precursor varnish " the ト レ ニ-ス " #3000 of Dong Li company (strain), regulated varnish solution and make acid chloride content become 1wt/vol%.
Then, handle the test piece 10 * 10cm (thickness 50 μ m) of the polyimide base material " ユ-ピ レ Star Network ス-S " of the emerging product of space portion (strain) with the 1%NaOH aqueous solution and the 1%HCl aqueous solution, with pure water clean, after the drying, apply above-mentioned varnish solution, dry under 120 ℃, obtain the base material that coating thickness is 4 μ m.
20% aqueous ethanolic solution is dripped on the above-mentioned base material,, use Cooper-Hewitt lamp irradiation ultraviolet radiation 3 minutes sandwiching under the state that forms the aqueous ethanolic solution film between the quartz plate.
Then, carry out similarly to Example 1 processing.
Embodiment 8
The acid chloride content of embodiment 7 is changed to 0.5wt/vol%, carry out same processing.The copper film of embodiment 7 and embodiment 8 is thick to be shown in Table 2 with stripping strength
Table 2
| Embodiment No. | Palladium coordination compound content wt/vol% | Ultraviolet irradiating dose mJ/cm 2 | The thick μ m of copper film | Stripping strength N/cm |
| 7 | 1.0 | 4500 | 24 | 14 |
| 8 | 0.5 | 4500 | 24 | 13.5 |
Embodiment 9
With polyimide base material " ユ-ピ レ Star Network ス-S " the Bian Geng of the emerging product of space portion (strain) of embodiment 1 Kapton " カ プ ト Application EN ", carry out same processing into East レ デ ユ Port Application (strain).The copper film of the electronic component-use base material that obtains is thick to be shown in Table 3 with stripping strength.
Table 3
| Embodiment No. | Palladium coordination compound content wt/vol% | Ultraviolet irradiating dose mJ/cm 2 | The thick μ m of copper film | Stripping strength N/cm |
| 9 | 1.0 | 4500 | 23 | 13.5 |
Embodiment 10
Mixed at polyimide resin precursor varnish " ト レ ニ-ス " moderate in the mixture of thermoplastic polyimide varnish " SPI-200N " of Nippon Steel chemistry (strain) to the Dong Li of embodiment 1 company (strain), add the nmp solution of palladium coordination compound, regulate varnish solution, make the content of palladium coordination compound become 1wt/vol%.
Then clean with pure water, on the polyimide base material " カ プ ト Application EN " (thickness 50 μ m) of dry eastern レ デ ユ Port Application (strain), apply above-mentioned varnish solution, in 120 ℃ down dry, obtain having the base material of the thin film layer that constitutes by polyimide resin precursor and thermoplastic polyimide of thickness 3 μ m.
20% aqueous ethanolic solution is dripped on the above-mentioned base material,, use Cooper-Hewitt lamp irradiation ultraviolet radiation 3 minutes sandwiching under the state that forms the aqueous ethanolic solution film between the quartz plate.The result that ultraviolet irradiation dosage is measured at the luxmeter " UV-02 " of making manufacturing of オ-Network is 7500mJ/cm
2
Below, carry out processing similarly to Example 1.The copper film of the electronic component-use base material that obtains is thick to be shown in Table 4 with stripping strength.
Table 4
| Embodiment No. | Palladium coordination compound content wt/vol% | Ultraviolet irradiating dose mJ/cm 2 | The thick μ m of copper film | Stripping strength N/cm |
| 10 | 1.0 | 7500 | 20 | 11.5 |
Embodiment 11
To dissolve the solution of commercially available Palladous chloride 5% aqueous solution among the NMP, added among polyimide resin precursor varnish " the ト レ ニ-ス " #3000 of Dong Li company (strain), regulated making Palladous chloride content become 1wt/vol%.Point of addition generation gelation so add nmp solvent again, is warmed to 80 ℃ when adding above-mentioned solution, and stir about made concentration reach even in 1 hour.
Below, carry out processing similarly to Example 1.The copper film of the electronic component-use base material that obtains is thick to be shown in Table 5 with stripping strength.
Table 5
| Embodiment No. | Palladium coordination compound content wt/vol% | Ultraviolet irradiating dose mJ/cm 2 | The thick μ m of copper film | Stripping strength N/cm |
| 11 | 1.0 | 4500 | 20 | 11 |
Embodiment 12
In NMP (2g), mix polyimide resin precursor varnish " the ト レ ニ-ス " #3000 (1g) and the palladium methyl ethyl diketone coordination compound of Dong Li company (strain), the viscosity of investigation solution changes.Its result as shown in Figure 3, has just mixed the back and do not seen big variation through the solution state after 30 minutes, but viscosity increases sharp thereafter, is judged as to have formed polymer complex compound.
Handle the test piece 10 * 10cm (thickness 50 μ m) of the polyimide base material " ユ-ピ レ Star Network ス-S " of the emerging product of space portion (strain) with the 1%NaOH aqueous solution and the 1%HCl aqueous solution, with pure water clean, after the drying, apply the mixing solutions of " ト レ ニ-ス " varnish and palladium methyl ethyl diketone coordination compound, after 120 ℃ of following dryings, at the ultraviolet ray (7500mJ/cm that cuts off irradiation Cooper-Hewitt lamp under the air state with moisture film
2), put into again be warmed to 65 ℃, be that the electroless plating nickel of reductive agent is bathed the table 6 that the results are shown in that " エ Application プ レ-ト Ni-426 " (pH=6～7) flood with the sodium hypophosphite of メ Le テ Star Network (strain).
Concentration in the so-called table is the concentration % of the palladium methyl ethyl diketone coordination compound of average varnish solution, and so-called meltage is the meltage of palladium methyl ethyl diketone coordination compound.In addition, when so-called solvability refers to above-mentioned solution gel, be warmed to 80 ℃, append NMP and make it to dissolve necessary NMP amount in order on polyimide base material, to apply.
Table 6
| Concentration (%) | Meltage (g) | NMP measures (g) | Solution state | Solvability | Plating |
| 1.0 | 0.01 | 2.0 | Gel | Dissolve with 12g | ○ |
| 0.5 | 0.005 | 2.0 | The frozen glue shape | Dissolve with 6g | ○ |
| 0.1 | 0.001 | 2.0 | Viscosity rises | Need not append | ○ |
Here, zero of plating means with 10～15 minutes specimen surface integral body and forms (not having inhomogeneous all the same) nickel plating well.
Embodiment 13
In NMP (2g), mix above-mentioned varnish solution (1g) and acid chloride, investigate the table 7 that the results are shown in that the viscosity of solution changes similarly to Example 12.Moreover, just mixed the back and do not seen big variation, but viscosity increases sharp thereafter, this means to have formed polymer complex compound through the solution state after 1 hour.
Concentration in the so-called table is the concentration % of the acid chloride of average varnish, and so-called meltage is the meltage of acid chloride.In addition, when solvability refers to above-mentioned solution gel, be warmed to 80 ℃, append NMP and make it to dissolve necessary NMP amount on polyimide base material, applying.
Table 7
| Concentration (%) | Meltage (g) | NMP measures (g) | Solution state | Solvability | Plating |
| 1.0 | 0.01 | 2.0 | Gel | Dissolve with 12g | ○ |
| 0.5 | 0.005 | 2.0 | The frozen glue shape | Dissolve with 6g | ○ |
| 0.1 | 0.001 | 2.0 | Viscosity rises | Need not append | ○ |
Embodiment 14
Varnish solution (1g) and 5% palladium chloride aqueous solution are mixed, investigate the table 8 that the results are shown in that the viscosity of solution changes similarly to Example 12.
Moreover, after so-called aggegation refers to varnish solution and 5% palladium chloride aqueous solution is mixed, hastily gelation situation.Judge it is that viscosity sharply increases, and has formed polymer complex compound by this change of state.
Concentration in the so-called table is the concentration % of the Palladous chloride of average varnish solution, and so-called meltage is the meltage of Palladous chloride.In addition, when so-called solvability refers to above-mentioned solution gel, be warmed to 80 ℃, append NMP and make it to dissolve necessary NMP amount in order on polyimide base material, to apply.
Table 8
| Concentration (%) | Meltage (g) | Solution state | Solvability | Plating |
| 5.0 | 0.05 | Aggegation | Dissolve with 4g | ○ |
| 1.0 | 0.01 | Aggegation | Dissolve with 2g | ○ |
Comparative example 1
In embodiment 1, irradiation ultraviolet radiation not, other carry out same operation.
Comparative example 2
In embodiment 2, irradiation ultraviolet radiation not, other carry out same operation.
Comparative example 3
In embodiment 7, irradiation ultraviolet radiation not, other carry out same operation.
Comparative example 4
In embodiment 11, irradiation ultraviolet radiation not, other carry out same operation.
Comparative example 5
In embodiment 1, cut off air without moisture film, be irradiation ultraviolet radiation in air, other carry out same operation.
Comparative example 6
In embodiment 1, do not adopt the imidization of heating, other carry out same operation.
Comparative example 7
In embodiment 3, do not adopt the imidization of heating, other carry out same operation.
Comparative example 1～7 the results are shown in table 9.Shown in comparative example, irradiation ultraviolet radiation not, or under the non-existent state of hydrogen donor during irradiation ultraviolet radiation, the palladium ion incomplete reduction becomes metallic palladium, can not form the clad substate metal level so cover processing by electroless plating.In addition, when not adopting the imidization of heating, the clad substate nuclear in the polyimide resin precursor layer is not fully caught, so the metal and the adhesion strength between the polyimide resin layer of electronic component-use base material (copper electroplating thickness 24 μ m) are low.
Table 9
| Comparative example No. | The electroless plating property covered | Electrolytic | Stripping strength | |
| 1 | × | × | - | |
| 2 | × | × | - | |
| 3 | × | × | - | |
| 4 | △ (having inhomogeneous) | × | - | |
| 5 | △ (having inhomogeneous) | × | - | |
| 6 | ○ | ○ | 0.3N/cm | |
| 7 | ○ | ○ | 0.25N/cm |
In the so-called stripping strength hurdle-, refer to complete non-cohesive coating layer, so stripping strength can't be measured.
Comparative example 8
In embodiment 12, palladium methyl ethyl diketone coordination compound is changed, use copper (II) methyl ethyl diketone coordination compound, the results are shown in the table 10 of the change in concentration of investigation solution.This time, the state of solution had not both observed viscosity to be changed and also not to observe gelation, does not change through viscosity also occurring after 24 hours.Can think, when using copper (II) methyl ethyl diketone coordination compound, the formation of coordination compound not take place.
Concentration in the so-called table is the concentration % of copper (II) the methyl ethyl diketone coordination compound of average varnish solution, and so-called meltage is the meltage of copper (II) methyl ethyl diketone coordination compound.
Table 10
| Concentration (%) | Meltage (g) | NMP measures (g) | Solution state |
| 1.0 | 0.01 | 3.0 | Aqueous |
| 0.5 | 0.005 | 3.0 | Aqueous |
| 0.1 | 0.001 | 3.0 | Aqueous |
Industrial applicibility
The present invention, owing to be that palladium compound is dispersed in the polyimide resin precursor, and be the polyimide resin precursor solution that palladium compound and polyimide resin precursor form complex, so uniform polyimide resin precursor layer can be provided.
The present invention still, between polyimide base material and overlay coating, has the such structure of polyimide resin layer that forms with above-mentioned polyimide resin precursor solution, so can provide the adhesion strength of clad substate metal level and polyimide resin very high electronic component-use base material.
And, the present invention still, make the polyimide resin precursor solution that contains palladium compound apply the dry polyimide resin precursor layer that forms at polyimide base material, irradiation ultraviolet radiation in the presence of hydrogen donor, after forming clad substate nuclear, process formation clad substate metal level by electroless plating, then after forming overlay coating or before forming, add the above-mentioned polyimide resin precursor layer of hot-imide, make polyimide resin layer, clad substate nuclear is present in the polyimide resin, so the very high electronic component-use base material of adhesion strength that makes clad substate metal level and polyimide resin owing to its anchoring effect can be provided.
Claims (7)
1. electronic component-use base material, it forms the clad substate that the polyimide resin precursor solution of coordination compound forms by palladium compound and polyimide resin precursor and examines by form using on polyimide base material, on this clad substate nuclear, form and cover the clad substate metal level of handling formation, on this clad substate metal level, form overlay coating and form by electroless plating.
2. according to the electronic component-use base material of claim 1 record, it is characterized in that polyimide resin precursor is at least a polyimide resin precursor varnish that contains polyamic acid, polyamic acid derivative.
3. according to the electronic component-use base material of claim 1 record, it is characterized in that palladium compound is palladium methyl ethyl diketone coordination compound or organic acid palladium salt.
4. the manufacture method of an electronic component-use base material, it is characterized in that, by on polyimide base material, apply dry palladium compound and be evenly dispersed in the polyimide resin precursor and palladium compound and polyimide resin precursor form the polyimide resin precursor solution of coordination compound, form the polyimide resin precursor layer; Then in the presence of the hydrogen donor to this precursor layer irradiation ultraviolet radiation, form clad substate nuclear after, cover processing by electroless plating and on this clad substate nuclear, form the clad substate metal level; And then on this clad substate metal level, form overlay coating, and before overlay coating forms the back or forms, above-mentioned polyimide resin precursor layer is added hot-imide, make polyimide resin layer.
5. according to the manufacture method of the electronic component-use base material of claim 4 record, it is characterized in that polyimide resin precursor is at least a polyimide resin precursor varnish that contains polyamic acid, polyamic acid derivative.
6. according to the manufacture method of the electronic component-use base material of claim 4 record, it is characterized in that palladium compound is palladium methyl ethyl diketone coordination compound or organic acid palladium salt.
7. according to the manufacture method of the electronic component-use base material of claim 4 record, it is characterized in that the hydrogen donor is water, alcohol or alcohol solution.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16339/2001 | 2001-01-24 | ||
| US16339/01 | 2001-01-24 | ||
| JP2001016339A JP2002030216A (en) | 2000-05-12 | 2001-01-24 | Polyimide resin precursor solution, substrate for electronic part using the solution and method for producing the substrate |
| PCT/US2001/011613 WO2001077749A1 (en) | 2000-04-11 | 2001-04-09 | Sterically stabilized second-order nonlinear optical chromophores |
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| Publication Number | Publication Date |
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| CN1487978A CN1487978A (en) | 2004-04-07 |
| CN1239622C true CN1239622C (en) | 2006-02-01 |
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| US7666471B2 (en) * | 2006-03-22 | 2010-02-23 | Mark Wojtaszek | Polyimide substrate and method of manufacturing printed wiring board using the same |
| JP5462631B2 (en) * | 2007-11-30 | 2014-04-02 | 三井化学株式会社 | Polyimide composite material and film thereof |
| CN102298998A (en) * | 2010-06-23 | 2011-12-28 | 比亚迪股份有限公司 | Insulating material and preparation method for the same |
| CN109246920B (en) * | 2017-06-08 | 2020-10-02 | 臻鼎科技股份有限公司 | Covering film and manufacturing method thereof |
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