JP3894668B2 - Laminated body of heat-resistant film with improved adhesion - Google Patents

Description

【００３３】
実施例８−１２
固形分（ポリアミック酸）に対して３重量％の１，２−ジメチルイミダゾ−ルを添加した（実施例８−１１）あるいは添加しない（実施例１２）ポリアミック酸溶液を使用し、有機アルミニウム化合物塗布液としてアルミニウムトリアセチルアセトナ−トのトルエン溶液に代えて、表２に示す塗布液（塗布液▲１▼、塗布液▲２▼、塗布液▲３▼、あるいは塗布液▲４▼）とした他は実施例１に記載の方法と同様にして、アルミニウムを含有する厚み５０μｍのポリイミドフィルムを得た。
実施例８で得られたフィルムは、ＡＳＴＭ Ｄ−８８２で測定した弾性率が７３０ｋｇ／ｍｍ² 、引張強度が３５ｋｇ／ｍｍ² 、伸びが４０％であった。
また、他の実施例（９−１２）で得られたフィルムもほぼ同じ物性を示した。このようにして得られたフィルムの有機アルミニウム化合物塗布面を、常法により蒸着またはスパッタ加工し、さらにその上に電解メッキして１０μｍの銅層を形成した。
これらの積層体について、実施例１と同様にして評価した。
また、これらの操作を連続ロ−ルで行ない良好な結果が得られることを確認した。
各例において、１，２−ジメチルイミダゾ−ル添加／スパッタ−電解メッキの組み合わせが、表面の均一性が最も良好であった。
結果をまとめて表２に示す。
【００３４】
表２に於ける塗布液▲１▼、塗布液▲２▼、塗布液▲３▼、あるいは塗布液▲４▼は次の有機アルミニウム化合物溶液を意味する。
塗布液▲１▼：アルミニウムオキサイドステアレ−トトリマ−（川研ファインケミカル株式会社製、アルゴマ−１００Ｓ）の０．５％キシレン溶液
塗布液▲２▼：アルミニウムオキサイドステアレ−トトリマ−の０．０５％キシレン溶液
塗布液▲３▼：アルミニウムオキサイドオクチレ−トトリマ−（川研ファインケミカル株式会社製、アルゴマ−８００Ａ）の０．５％２−プロパノ−ル溶液
塗布液▲４▼：アルミニウムエチルアセトアセテ−トジイソプロピレ−ト（川研ファインケミカル株式会社製、ＡＬＣＨ）の３％ｎ−ジメチルアセトアミド（ＤＭＡｃ）溶液
【００３５】
【表２】

【００３６】
【発明の効果】
この発明によれば、簡単な操作によって、接着強度の大きい金属または金属酸化物の耐熱性フィルムの金属または金属酸化物積層体を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a laminate in which a metal or a metal oxide is directly laminated on a heat resistant film such as a polyimide film containing aluminum and having improved adhesiveness after completion of high-temperature heat treatment.
[0002]
[Prior art]
Polyimide films are widely used for electronic devices because they are excellent in thermal properties and electrical properties.
However, the polyimide film has a problem in that a large adhesive strength cannot be obtained with an adhesive usually used in the electronic field, and a laminate having a high peel strength cannot be obtained even if a metal layer is provided by metal deposition or sputtering. .
[0003]
Various attempts have been made to improve the low adhesion of the polyimide film.
For example, JP-A-4-261466, JP-A-6-299883, and JP-A-7-503984 disclose adhesiveness containing 0.02-1% by weight of a compound of tin, bismuth or antimony. Improved polyimide film is described.
However, these polyimide films may deteriorate electrical characteristics such as electrical insulation.
JP-A-59-86634 and JP-A-2-134241 describe a technique for improving adhesiveness of a polyimide film by plasma discharge treatment.
However, in this discharge treatment, the effect of improving the adhesiveness of the polyimide film may be insufficient, and a complicated post-treatment process is required and productivity is low.
Further, JP-A-1-214840 describes a technique for improving adhesion by forming an aluminum chelate compound film of a polyimide film.
However, according to the above publication, high-temperature heat treatment is required after the step that exhibits adhesiveness, and it cannot be used in the general electronic device field of polyimide films.
[0004]
[Problems to be solved by the invention]
The object of the present invention is that it can be used in the electronic field while maintaining excellent properties such as thermal properties, physical properties, and electrical properties of a heat-resistant film such as a polyimide film, and has good adhesion. It is to provide a laminate in which a metal or metal oxide is directly laminated on a heat resistant film.
[0005]
[Means for solving problems]
That is, this invention provides a aluminum content of the film 1-1000Ppm, one or directly on both sides of the polyimide film adhesion improved thickness obtained by completing the heat treatment 10-125Myuemu, vacuum deposition method , electron beam - a metal or metal oxide is laminated in a thickness less than 1μm by physicochemical lamination process selected from beam evaporation or sputtering, preparation of the laminate for forming a metal plating layer of 1~40μm on this About.
[0006]
The heat-resistant film with improved adhesion in the present invention is preferably prepared by adding an aluminum compound to a film-forming polyamic acid solution and casting the dope solution uniformly dissolved, followed by drying by heating or polyamic acid. By heating a dry film containing an aluminum component obtained by applying a solution containing an aluminum compound to a self-supporting film obtained from the solution and drying it at a temperature of 420 ° C. or higher to complete imidization A polyimide film having an aluminum content of 1-1000 ppm is obtained.
[0007]
There is no restriction | limiting in particular as a polyimide which comprises the said polyimide film, For example, the arbitrary aromatic polyimides obtained from aromatic tetracarboxylic dianhydride and aromatic diamine can be used. Those in which some of these are replaced with alicyclic tetracarboxylic dianhydrides or aliphatic diamines can also be used.
In addition, some of these were replaced with aminodicarboxylic acids such as 4-aminophthalic acid, 4-amino-5-methylphthalic acid, 4- (3,3′-dimethyl-4-anilino) phthalic acid, and reacted. There may be.
[0008]
Examples of the aromatic tetracarboxylic dianhydride include 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes simply referred to as s-BPDA), pyromellitic acid 2 Anhydride, benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride (oxydiphthalic dianhydride) and the like can be mentioned.
Examples of the aromatic diamine include paraphenylene diamine and 4,4′-diaminodiphenyl ether. Some of them are 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 1,4-bis (4- Aminophenoxy) benzene, 4,4′-bis (4-aminophenyl) diphenyl ether, 4,4′-bis (4-aminophenyl) diphenyl sulfone, 4,4′-bis (4-aminophenyl) diphenyl Sulfide, 4,4′-bis (4-aminophenyl) diphenylmethane, 4,4′-bis (4-aminophenoxy) diphenyl ether, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4, 4′-bis (4-aminophenoxy) diphenyl sulfide, 4,4′-bis (4-aminophenoxy) diphenylmethane, 2,2-bis [ Flexible aromatic diamines having a plurality of benzene rings such as-(aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-diaminobutane, , 6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, aliphatic diamines such as 1,12-diaminododecane, and diamines such as xylenediamine.
[0009]
In particular, as polyimide, polyimide obtained from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and paraphenylenediamine, pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyl Aromatic tetracarboxylic acid component of teturacarboxylic dianhydride or benzophenonetetracarboxylic dianhydride, paraphenylenediamine or paraphenylenediamine (sometimes abbreviated as PPD), and 4,4′-diaminodiphenyl ether ether with (sometimes abbreviated as DADE) range polyimides prepared from an aromatic diamine component of the low linear thermal expansion coefficient (typically 50-250 ° C. ^{in, 1 × 10 -5 -2 × 10} -5 cm / cm / ° C.). In the case of a copolymer, the PPD / DADE (molar ratio) is preferably 100 / 0-15 / 85. Polyimide can be achieved by homopolymerization, random polymerization, block polymerization, or any method in which two or more kinds of polyamic acids are synthesized in advance and the polyamic acid solution is mixed to complete the reaction.
A film having an amide bond, such as a polyamideimide film, can also be used as the heat resistant film.
[0010]
The aluminum ratio (in terms of aluminum metal) of the heat-resistant film needs to be 1-1000 ppm, particularly 4-1000 ppm.
The proportion of aluminum in the film means the average value in the film.
If the amount of aluminum in the heat-resistant film is 1 ppm or less, the improvement in adhesion is not sufficient, and if it is more than 1000 ppm, the mechanical properties of the heat-resistant film are rather lowered, and the adhesion is also lower than that in the range. This is not preferable.
[0011]
The heat-resistant film with improved adhesiveness uses, for example, each of the above components, and a substantially equimolar amount of a diamine component and tetracarboxylic dianhydride is reacted in an organic solvent to obtain a polyamic acid solution ( A part of the polyamic acid solution may be imidized as long as a uniform solution state is maintained, and an aluminum compound is added to the polyamic acid solution to uniformly dissolve the dope solution on the support. 420. A dry film peeled off from a support after heat drying, or a dry film containing an aluminum component obtained by applying a solution containing an aluminum compound to a self-supporting film obtained from a polyamic acid solution and then drying, 420 More than ℃, especially 430-520 ℃, preferably heated for about 2-30 minutes to complete imidization, the aluminum content of the film The thickness is 1-1000ppm 7-125μm, preferably 10-125Myuemu, it is particularly preferable to obtain a polyimide film having improved adhesion by forming a polyimide film of about 25-125Myuemu.
[0012]
As said aluminum compound, an aluminum compound soluble in a polyamic acid solution can be used conveniently.
These aluminum compounds include, for example, aluminum hydroxide, aluminum monoethyl acetate diisopropylate, aluminum diethyl acetate monoisopropylate, aluminum triacetylacetonate, aluminum triethylacetoacetate, aluminum isopropylate. And organoaluminum compounds such as aluminum oxide butyl trimer, aluminum oxide stearate trimer, aluminum oxide isopropoxide trimer, aluminum oxide laurate trimer, etc. As the organoaluminum compound, aluminum triacetylacetonate is preferable.
[0013]
In the above method, when a solution containing an aluminum compound is applied to the self-supporting film, the concentration of the applied aluminum compound is about 0.01-5% by weight, particularly about 0.02-5% by weight. Is preferred.
The solvent used in the coating solution is not particularly limited, and includes alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, alicyclic hydrocarbon, ketone solvent, ether solvent, and amide solvent. Can be used.
[0014]
The self-supporting film is prepared by, for example, reacting the acid component and the diamine component in an organic solvent at a temperature of about 100 ° C. or less, particularly 20-60 ° C., to obtain a polyamic acid solution. -It can be used as a dope solution, cast on the support, dried to about 70-200 ° C to form a thin film, and peeled off from the support.
In order to facilitate this peeling, an organophosphorus compound such as triphenyl phosphite, triphenyl phosphate, alkyl phosphate ester salt or the like is not added to the solid content (polymer) concentration during polyamic acid polymerization. 0.05 to 1% of range can be added.
[0015]
The organic solvent used for producing the polyamic acid is N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, N-methylcaprolactam etc. are mentioned. These organic solvents may be used alone or in combination of two or more.
[0016]
In addition, a basic organic compound can be added to the raw material solution for the purpose of promoting the imidization. For example, imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, triethylamine and the like are 0.1 to 10% by weight with respect to the solid content concentration during polyamic acid polymerization. Can be used in proportions.
[0017]
The metal or metal oxide laminate of the present invention is the heat-resistant film, preferably the polyimide film (which may be a plate or a molded article having various other shapes). -Adhering metals or metal oxides directly on one or both sides of heat-resistant films and molded bodies such as polyimide films containing 1000ppm and improved heat treatment, such as vapor deposition, sputtering, plating, etc. It is obtained by laminating by a laminating method that does not use an agent.
[0018]
The metal or metal oxide vapor deposition can be particularly suitably performed by a physicochemical vapor deposition method such as a vacuum vapor deposition method, an electron beam vapor deposition method, or a sputtering method. As a vapor deposition method, the degree of vacuum is about 10 ⁻⁷ −10 ⁻² Torr, the vapor deposition rate is about 50 to 5000 km / sec, and the temperature of the vapor deposition substrate (film) is about 20 to 600 ° C. Preferably there is. In the sputtering method, the RF magnet sputtering method is particularly preferable, and the degree of vacuum at that time is 1 Torr or less, particularly about 10 ⁻³ -10 ⁻² Torr, the substrate temperature is 200 to 450 ° C. It is preferable that the forming temperature is about 0.5 to 500 kg / sec.
[0019]
The thickness of the obtained metal or metal oxide layer (film) is usually about 1 μm or less, and a thicker film is preferably formed thereon. The thickness is preferably about 1-40 μm.
[0020]
As the material of the metal film or metal oxide film, metals such as copper or copper alloy, aluminum, tin, tin alloy, palladium, or these metal oxides are suitable.
Chromium, titanium, palladium or the like may be used as the underlayer, and copper may be used as the surface layer.
In addition, a metal plating layer may be formed on the metal or metal oxide thus obtained, and examples of the material of the metal plating layer include copper, copper alloy, silver, and the like. As a method, either an electroless plating method or an electrolytic plating method may be used.
In addition, it is preferable that the metal thin film is formed in a continuous roll including the sputtering and vapor deposition methods.
[0021]
The laminate obtained by the present invention maintains the physical properties of a heat-resistant film itself such as a polyimide film by a simple operation and has good adhesive strength, so that it can be suitably used as a material in the electronic field. .
[0022]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.
The thermal expansion coefficient was measured at a heating rate of 10 ° C./min.
The aluminum content in the polyimide film was measured by the following ICP emission analysis.
A film sample (about 1 g) was dissolved by acidization after combustion carbonization and ashing, and analyzed by ICP emission spectrometry (plasma excitation emission spectrometry).
MARK-2 type).
[0023]
Example 1-2
To a 300 ml glass reaction vessel equipped with a polyimide film-forming dope synthesis stirrer, nitrogen inlet tube and reflux tube, 183 g of N, N-dimethylacetamide and 0.1 g of phosphoric acid compound (Separ 365-100 Chukyo) (Oil Co., Ltd.) was added, and 10.81 g (0.1000 mol) of paraphenylenediamine was added under stirring and nitrogen flow, and the mixture was kept at 50 ° C. and completely dissolved. To this solution, 29.229 g (0.09935 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was gradually added while paying attention to heat generation. The reaction continued for hours. Thereafter, 0.2381 g (0.00065 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic acid dihydrate was dissolved. The resulting polyamic acid solution was a brown viscous liquid, and the solution viscosity at 25 ° C. was about 1500 poise.
As a single layer (50 μm) of a polyimide film separately produced from this dope, the thermal expansion coefficient at 50-200 ° C. was 1.5 × 10 ⁻⁵ cm / cm / ° C.
[0024]
The polyamic acid solution was cast on a glass substrate, dried at 150 ° C. for 10 minutes, peeled off from the substrate, restrained on the frame, and aluminum triacetylacetonate having the concentrations shown in Table 1 After applying a toluene solution, the mixture was heat-treated at 200 ° C. for 3 minutes, 300 ° C. for 3 minutes, and 480 ° C. for 4 minutes to obtain a polyimide film having a thickness of 50 μm.
[0025]
Manufacture of Laminate After the polyimide film surface (organoaluminum compound coated surface) was subjected to normal cleaning treatment, a copper thin film was formed by an electron beam evaporation method.
After the film cut into the holder size is placed in the vapor deposition apparatus, the substrate temperature is 150 ° C., the degree of vacuum is 2 × 10 ⁻⁴ Pa or less, the raw material copper purity is ⁴ N, and the vapor deposition rate is about 10-25 angstrom / second. A copper film with a thickness of 2 μm was deposited.
Further, a 10 μm copper layer was formed thereon by electrolytic plating. The laminate was immersed in 2N hydrochloric acid for 5 minutes, and then the T-peel strength (25 ° C.) was measured.
The results are summarized in Table 1.
[0026]
Example 3
A dope in which the amount of aluminum hydroxide shown in Table 1 was added to the polyamic acid solution and uniformly dissolved was cast on a glass substrate, dried at 150 ° C. for 10 minutes, and peeled off from the substrate. Restrained on the frame, heat treatment was performed at 200 ° C. for 3 minutes, 300 ° C. for 3 minutes, and 480 ° C. for 4 minutes to obtain a polyimide film having a thickness of 50 μm.
Using this film, a laminate was obtained in the same manner as in Example 1.
The results are summarized in Table 1.
[0027]
Example 4-5
The polyamic acid solution was cast on a glass substrate, dried at 150 ° C. for 10 minutes, peeled off from the substrate, restrained on the frame, and an aluminum chelate compound having the concentrations shown in Table 1 ( After applying a DMAc solution of Kawaken Fine Chemical Co., Ltd. (ALCH), heat treatment was performed at 200 ° C. for 3 minutes, 300 ° C. for 3 minutes, and 480 ° C. for 4 minutes to obtain a polyimide film having a thickness of 50 μm.
Using this film, a laminate was obtained in the same manner as in Example 1.
The results are summarized in Table 1.
[0028]
Example 6
A dope in which the amount of aluminum hydroxide shown in Table 1 was added to the polyamic acid solution and uniformly dissolved was cast on a glass substrate, dried at 150 ° C. for 10 minutes, and peeled off from the substrate. After constraining on the frame and applying a toluene solution of aluminum triacetylacetonate with the concentrations shown in Table 1, heat treatment was performed at 200 ° C for 3 minutes, 300 ° C for 3 minutes, and 480 ° C for 4 minutes. Thus, a polyimide film having a thickness of 50 μm was obtained.
Using this film, a laminate was obtained in the same manner as in Example 1.
The results are summarized in Table 1.
[0029]
Example 7
The polyamic acid solution was cast on a glass substrate, dried at 150 ° C. for 10 minutes, peeled off from the substrate, restrained on the frame, and an aluminum chelate compound having the concentrations shown in Table 1 ( After applying a DMAc solution of Kawaken Fine Chemical Co., Ltd. (ALCH), heat treatment was performed at 200 ° C. for 3 minutes, 300 ° C. for 3 minutes, and 480 ° C. for 4 minutes to obtain a polyimide film having a thickness of 25 μm.
Using this film, a laminate was obtained in the same manner as in Example 1.
The results are summarized in Table 1.
[0030]
Moreover, when the tensile strength, elongation, bending resistance, and electrical insulation were confirmed about the polyimide film obtained in each Example, it was substantially equivalent to the conventionally well-known polyimide film.
[0031]
Comparative Example 1
A polyamic acid solution is cast-coated on a glass substrate, dried at 150 ° C. for 10 minutes, peeled off from the substrate and restrained on the frame, restrained on the frame at 200 ° C. for 3 minutes, 300 ° C. for 3 minutes, and 480 ° C. for 4 minutes. A polyimide film having a thickness of 50 μm was obtained by heat treatment.
Using this film, a laminate was obtained in the same manner as in Example 1.
The results are summarized in Table 1.
[0032]
[Table 1]

[0033]
Examples 8-12
Application of organoaluminum compound using polyamic acid solution with or without adding 3% by weight of 1,2-dimethylimidazole to solid content (polyamic acid) (Example 8-11) Instead of the toluene solution of aluminum triacetylacetonate as the solution, the coating solution shown in Table 2 (coating solution (1), coating solution (2), coating solution (3), or coating solution (4)) was used. Others were the same as the method described in Example 1, and a polyimide film containing aluminum and having a thickness of 50 μm was obtained.
The film obtained in Example 8 had an elastic modulus measured by ASTM D-882 of 730 kg / mm ² , a tensile strength of 35 kg / mm ² , and an elongation of 40%.
Moreover, the film obtained in the other Example (9-12) also showed substantially the same physical properties. The organoaluminum compound-coated surface of the film thus obtained was deposited or sputtered by a conventional method, and further electroplated thereon to form a 10 μm copper layer.
These laminates were evaluated in the same manner as in Example 1.
Also, it was confirmed that good results were obtained by performing these operations in a continuous roll.
In each example, the combination of 1,2-dimethylimidazole addition / sputter-electrolytic plating had the best surface uniformity.
The results are summarized in Table 2.
[0034]
The coating solution (1), coating solution (2), coating solution (3), or coating solution (4) in Table 2 means the following organoaluminum compound solution.
Coating solution {circle around (1)}: 0.5% xylene solution coating solution of aluminum oxide steer trimmer (Algoma-100S, manufactured by Kawaken Fine Chemical Co., Ltd.) {2}: 0.05% of aluminum oxide steer trimmer Xylene solution coating solution {circle around (3)}: 0.5% 2-propanol solution coating solution of aluminum oxide octylate trimer (Arkoma 800A, manufactured by Kawaken Fine Chemical Co., Ltd.) {circle around (4)}: Aluminum ethyl acetoacetate diisopropylate -3% n-dimethylacetamide (DMAc) solution of G (ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.)
[Table 2]

[0036]
【The invention's effect】
According to this invention, a metal or metal oxide laminate of a metal or metal oxide heat-resistant film having a high adhesive strength can be obtained by a simple operation.

Claims (3)

The film has an aluminum content (in terms of aluminum metal) of 1-1000 ppm, and a vacuum deposition method directly on one or both sides of a polyimide film having an improved adhesiveness of 10-125 μm obtained by completing the heat treatment, A method for producing a laminate in which a metal or metal oxide is laminated to a thickness of 1 μm or less by a physicochemical lamination method selected from an electron beam vapor deposition method or a sputtering method, and a metal plating layer of 1 to 40 μm is formed thereon. The polyimide film is casted with an aluminum compound added to the film-forming polyamic acid solution and uniformly dissolved, and then heated to dry, or the self-supporting film obtained from the polyamic acid solution contains an aluminum compound. The process for producing a laminate according to claim 1 , wherein the imidization is completed by heating a dry film containing an aluminum component obtained by applying the solution and then drying. Polyimide ^{film, 1 × 10 -5 -2 × 10} -5 cm / cm / ℃ preparation of laminate according to claim 1, wherein the linear a thermal expansion coefficient (50-250 ° C.) of.