JP2005036132A - Adhesive adjuvant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive adjuvant composition providing excellent adhesive strength to a polyimide film or the like without reducing mechanical characteristics, and useful in an electric material field. <P>SOLUTION: The adhesive adjuvant composition contains a phenolic hydroxy group-containing polyamic acid having a structure represented by formula (A) (wherein, R<SB>1</SB>is an aromatic group; n is the average number of substituents, and a positive number of 1-4; and R<SB>2</SB>is a tetravalent aromatic group) and a solvent. The polyimide film treated with the adhesive adjuvant composition is also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an adhesion aid composition containing a phenolic hydroxyl group-containing polyamic acid and a solvent.

  Usually, polyimide film is bonded to metal foil (mainly copper foil), metal is deposited, plated, or sputtered, or polyimide precursor is coated on metal foil and imidized by heating, etc. Fabricate copper-clad laminates, etc., and process double-sided copper-clad laminates obtained by bonding polyimide films with adhesives, and use them as base films for flexible printed wiring boards and multilayer printed wiring boards . However, the conventional polyimide film has a problem of poor surface adhesion, and as such causes a product defect. For this reason, for the purpose of improving the adhesion of the surface of the polyimide film, the film surface is subjected to corona discharge treatment or plasma treatment to impart hydrophilicity and used (Patent Document 1). Moreover, in order to roughen the surface of a polyimide film, the method of adding an inert particle to a precursor or carrying out the chemical | medical solution process of the film surface is known (patent document 2). However, since the surface of the film is subjected to corona discharge treatment or plasma treatment to impart hydrophilicity to the surface and at the same time the surface is brittle and easily peels off, the adhesive force cannot be essentially improved. In addition, the roughening of the film surface is usually less effective in the case of polyimide, which not only complicates the steps for film production or processing, but also reduces the strength and electrical characteristics of the film.

JP 05-279497 A Japanese Patent Laid-Open No. 10-095847 JP-A-08-124918

  An object of the present invention is to provide an adhesion assistant composition that is excellent in adhesive strength and useful in the field of electrical materials for polyimide films and the like without deteriorating mechanical properties.

As a result of diligent research, the present inventors have achieved excellent adhesive properties between films, adhesives to other adhesives and adhesive layers, and reduced excellent mechanical properties inherent to the films. The present invention has also been completed by finding a method of producing an adhesive auxiliary composition that is not allowed to be produced and a film that is excellent in adhesion using the composition. That is, the present invention
(1) Adhesive adjuvant composition containing a phenolic hydroxyl group-containing polyamic acid and a solvent (2) The phenolic hydroxyl group-containing polyamic acid is represented by the following formula (A)

(In formula (A), R ₁ represents an aromatic group, n is the average number of substituents and represents a positive number of 1 to 4. R ₂ represents a tetravalent aromatic group. X is the average degree of polymerization. And represents a positive number of 10 to 1,000.) The adhesion auxiliary composition according to the above (1) having a structure represented by:
(3) The adhesive auxiliary composition according to (1) or (2) above, which contains a polyimide precursor other than the phenolic hydroxyl group-containing polyamic acid, (4) any one of (1) to (3) above. A film (5) obtained by heating the adhesion assistant composition of (5) obtained by applying the adhesion assistant composition according to any one of (1) to (3) above to a polyimide precursor and heating it. Film (6) Single-sided copper-clad laminate having the film according to (4) or (5) (7) Double-sided copper-clad laminate having the film according to (4) or (5) (8) Above (4) Or the board | substrate for flexible printed wiring which has the film of (5) description (9) It is related with the board | substrate for multilayer printed wiring which has the film of the said (4) or (5) description.

  The adhesion adjuvant composition of this invention is excellent in workability, since it greatly improves the adhesion to a polyimide film or the like that originally has poor adhesion and is easy to adhere to an epoxy resin or the like. In addition, since the excellent mechanical properties of the adherend film are not deteriorated, it can be widely used in the production of multilayer wiring boards, and is extremely useful in the field of electrical materials such as adhesives and substrates.

  The adhesion aid composition of the present invention comprises a phenolic hydroxyl group-containing polyamic acid and a solvent as essential components, and the phenolic hydroxyl group-containing polyamic acid is particularly limited as long as it has a phenolic hydroxyl group in the molecular structure of the polyamic acid. The following formula (1)

(In formula (1), R ₁ represents an aromatic group, n represents an average number of substituents and represents a positive number of 1 to 4. R ₂ represents a tetravalent aromatic group.) Phenolic hydroxyl group-containing polyamic acid having The R ₁ group in the segment of the formula (1) is not particularly limited as long as it is an aromatic group having a phenolic hydroxyl group, but the following formula (2)

(In Formula (2), R ₃ represents a direct bond or a bond composed of 0 to 6 carbon atoms that may include O, S, P, F, and Si, and a, b, and c are the average number of substituents, Each of them represents a positive number of 1 to 4). The R ₂ group in the segment of the formula (1) is not particularly limited as long as it is an aromatic group, but the following formula (3)

(In formula (3), R ₄ represents a direct bond or a bond composed of 0 to 6 carbon atoms that may contain O, S, P, F, and Si). It is preferable to contain.

  Among the polyamic acids having such segments, in the present invention, all the segments are compounds of formula (1), that is, the following formula (A)

(In formula (A), R ₁ , R ₂ and n represent the same meaning as in formula (1). X represents the average degree of polymerization and represents a positive number of 10 to 1,000, preferably 50 to 500. .)
The compound represented by these is preferable. In the present invention, the polyamic acid preferably has a weight average molecular weight of 10,000 to 1,000,000.

  The above-mentioned phenolic hydroxyl group-containing polyamic acid in the adhesion aid composition of the present invention is usually equimolar to a phenolic hydroxyl group-containing diamine component, optionally other diamine component, and a tetracarboxylic acid component in a solvent under a nitrogen stream. The tetracarboxylic acid component is preferably reacted in an amount of 0.90 to 1.1 mol per 1 mol of the total diamine component.

  The phenolic hydroxyl group-containing diamine components used include diaminophenol, diaminoresorcin, diaminodihydroxybiphenyl, bis (aminohydroxyphenyl) ether, bis (aminohydroxyphenyl) methane, bis (aminohydroxyphenyl) propane, and bis (aminohydroxy). Phenyl) hexafluoropropane, bis (aminohydroxyphenyl) sulfoxide, diaminohydroxynaphthalene, diaminodihydroxynaphthalene and the like.

  Specific examples of other diamine components that can be used in this case include phenylenediamine, diaminotoluene, diaminoxylene, diaminomesitylene, diaminodurene, diaminoazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylenedianiline , Methylene bis (methylaniline), methylene bis (dimethylaniline), methylene bis (methoxyaniline), methylene bis (dimethoxyaniline), methylene bis (ethylaniline), methylene bis (diethylaniline), methylene bis (ethoxyaniline), methylene bis (diethoxyaniline), Isopropylidene dianiline, hexafluoroisopropylidene dianiline, diaminobenzophenone, di Mino dimethyl benzophenone, diaminoanthraquinone, diaminodiphenyl thioether, diaminodiphenyl dimethyl diphenyl thioether, diaminodiphenyl sulfone, and diaminodiphenyl sulfoxide, diaminofluorene and the like.

  Specific examples of tetracarboxylic acid components used in the reaction include pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, diphenyl sulfone. Tetracarboxylic dianhydride, methylene diphthalic anhydride, isopropylidene diphthalic anhydride, hexafluoroisopropylidene diphthalic anhydride, dimethyldiphenylsilane tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride Etc.

  The solvent used in the reaction for producing the phenolic hydroxyl group-containing polyamic acid and the solvent contained in the adhesion aid composition of the present invention may be the same or different, but the phenolic hydroxyl group-containing polyamic acid is taken out after the reaction. However, it is preferably the same because it can be used as an adhesion assistant composition. The solvent is not particularly limited as long as it can dissolve the phenolic hydroxyl group-containing polyamic acid, but N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl Caprolactam, N, N-dimethylimidazolidone, dimethyl sulfoxide, tetramethylurea, aprotic polar solvents such as pyridine, alcohol solvents such as methanol, ethanol, propanol, butanol, toluene, xylene, hexane, cyclohexane, heptane, etc. Nonpolar solvent, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, caprolactone, butyrolactone, valerolactone, caprolactam, butyrolactam, valerolactam, tetrahydrofuran, di Lime, dioxane or the like trioxane, or include a mixture of these solvents, among which N- methyl-2-pyrrolidone, N, N- dimethylacetamide, N, N- dimethylformamide is preferred.

The solvent is preferably used in an amount that makes a solution in which the phenolic hydroxyl group-containing polyamic acid is dissolved in an amount of 5 to 50% by weight, preferably 10 to 30% by weight.
The adhesion aid composition of the present invention may further contain a polyimide precursor other than the phenolic hydroxyl group-containing polyamic acid. The polyimide precursor that can be used is not particularly limited in its structure, and can be obtained in the same manner as the above-mentioned phenolic hydroxyl group-containing polyamic acid by reacting a tetracarboxylic acid component and a diamine component in an approximately equimolar amount. Specific examples of the diamine component and the tetracarboxylic acid component that can be used here include the other diamine component and the tetracarboxylic acid component, and the weight average molecular weight is preferably 10,000 to 1,000,000. . The polyimide precursor is easy to handle a solution in which 0 to 50% by weight, preferably 0 to 30% by weight, is dissolved in the adhesion aid composition.

  In addition, various additives can be added to the adhesion aid composition of the present invention within a range that does not impair the adhesiveness. For example, organic or inorganic pigments, dyes, leveling agents, antifoggants, antifade Agent, antihalation agent, optical brightener, surfactant, plasticizer, flame retardant, antioxidant, filler, antistatic agent, antifoaming agent, flow control agent, imidation catalyst, accelerator, dehydrating agent , Retarders, light stabilizers, photocatalysts, fungicides, antibacterial agents, low dielectric materials, conductors, magnetic materials, layered minerals, thermal decomposable compounds, etc. Later imidization is promoted, and a polyimide film can be obtained under relatively mild conditions.

  The adhesion adjuvant composition of this invention is obtained by mixing each said component uniformly by a predetermined ratio. Moreover, the usage method is apply | coated to a board | substrate so that it may become desired imide film thickness, and it is 5-180 minutes drying at 50-150 degreeC, and produces a phenolic hydroxyl group containing polyamic-acid film, Then, 200-under nitrogen stream. It heat-processes for 20 to 300 minutes at 500 degreeC, and is set as a whole surface adhesive film. Alternatively, a polyimide precursor solution other than a phenolic hydroxyl group-containing polyamic acid is applied to a substrate so as to have a desired imide film thickness, and dried at 50 to 150 ° C. for 5 to 180 minutes to produce a polyimide precursor film, on which It is also possible to produce a surface-adhesive film by applying an adhesion aid composition and further drying at 50 to 150 ° C. for 5 to 180 minutes, followed by heat treatment at 200 to 500 ° C. for 20 to 300 minutes in a nitrogen stream. . Further, in a system in which a catalyst or a dehydrating agent is added to a polyimide precursor, heat treatment can be performed at a relatively low temperature or in a short time.

  The substrate is not particularly limited as long as it can withstand the above heat treatment, such as a glass substrate, copper foil, aluminum foil, stainless steel substrate, drum, endless belt, etc. can get. Moreover, it is preferable to apply | coat so that the application | coating thickness of an adhesion adjuvant composition may be 5-50 micrometers thickness as an obtained film thickness, Preferably it is 10-25 micrometers thickness.

The adhesive film of the present invention contains a phenolic hydroxyl group on the film surface, is polar, and is reactive. Therefore, it reacts and bonds particularly well with adhesive compositions, adhesive films and the like containing various epoxy compounds, and is excellent in adhesive strength. For example, a double-sided copper-clad laminate having excellent adhesive strength can be obtained by bonding the film surfaces of the single-sided copper-clad laminate described above via an epoxy compound-containing adhesive composition. The epoxy compound-containing adhesive composition that can be used here includes an epoxy compound containing two or more epoxy groups, a curing agent thereof, and a curing accelerator, an ion supplementing agent, an inorganic filler, a solvent, and the like as necessary. There is no particular limitation as long as it is used as an adhesive for materials used in the electric / electronic field such as copper-clad laminates. For example, as an epoxy compound, a bisphenol type epoxy resin such as a bisphenol A type epoxy resin; a novolak type epoxy resin such as a phenol novolak type epoxy resin, a cresol novolak type epoxy resin or a phenol-bifevir novolak type epoxy resin; a phenol aralkyl type epoxy resin And epoxy resins such as bisphenol A; novolak resins such as phenol novolac resin, cresol novolac resin or phenol-bifevir novolac resin; and adhesive compositions mainly composed of a curing agent such as phenol aralkyl.
Similarly, when the copper-clad laminate is further processed, a flexible printed wiring board having excellent adhesive strength is obtained, and a multilayer printed wiring board is obtained by multilayering the same.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In addition, the characteristic measuring method of the film in an Example is as follows.
(Measurement of tensile modulus)
The film was measured according to ASTM D882 using a Tensilon tester (manufactured by Toyo Baldwin).
(Measurement of peel strength of double-sided copper-clad laminate)
The double-sided copper-clad laminate was measured according to JIS C6481 using a Tensilon tester (manufactured by Toyo Baldwin).

Example 1
In a 500 ml reactor equipped with a thermometer, a reflux condenser, a powder inlet, a nitrogen inlet, and a stirrer, 46.45 g (0.200 mol) of bis (3-amino-4-hydroxyphenyl) ether, 360.30 g of N-methyl-2-pyrrolidone was charged and stirred at room temperature while flowing dry nitrogen to dissolve the solid content. Thereafter, 43.63 g (0.200 mol) of pyromellitic dianhydride was added from the powder introduction port in about 30 minutes while keeping the inside of the reactor at 45 ° C. or lower. The mixture was further reacted for 18 hours. After completion of the reaction, pressure filtration was performed using a Teflon (registered trademark) filter having a pore diameter of 3 μm, and the following formula (4)

(M in the formula (4) is the average degree of polymerization, and the weight average molecular weight is 82,000.) The phenolic hydroxyl group-containing polyamic acid represented by 20% by weight was dissolved in N-methyl-2-pyrrolidone. The adhesion adjuvant composition of this invention was obtained.

Example 2
In a 500 ml reactor equipped with a thermometer, a reflux condenser, a powder inlet, a nitrogen inlet, and a stirrer, 41.81 g (0.180 mol) of bis (3-amino-4-hydroxyphenyl) ether, 379.00 g of N-methyl-2-pyrrolidone was charged and stirred at room temperature while flowing dry nitrogen to dissolve the solid content. Thereafter, 52.96 g (0.180 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added from the powder inlet in about 30 minutes while maintaining the inside of the reactor at 45 ° C. or lower. After the addition, the inside of the reactor was further reacted at 35 ° C. or lower for 18 hours. After completion of the reaction, pressure filtration was performed using a Teflon (registered trademark) filter having a pore size of 3 μm, and the following formula (5)

(M in formula (5) is the average degree of polymerization and the weight average molecular weight is 120,000.) The phenolic hydroxyl group-containing polyamic acid represented by 20% by weight was dissolved in N-methyl-2-pyrrolidone. The adhesion adjuvant composition of this invention was obtained.

Example 3
Using the automatic applicator (manufactured by Yasuda Seiki Seisakusho), the adhesion assistant composition obtained in Example 1 was coated on an 18 μm-thick electrolytic copper foil (manufactured by Japan Energy Co., Ltd.) so that the thickness after coating was 125 μm. And then dried at 130 ° C. for 10 minutes. Thereafter, the temperature was raised from 130 ° C. to 350 ° C. in a nitrogen stream over 2 hours, and further imidized by heat treatment at 350 ° C. for 2 hours to obtain an adhesive single-sided copper-clad laminate of the present invention. The film obtained by etching the copper foil had a thickness of 22 μm and a tensile modulus of 3.6 GPa.

Example 4
In Example 3, the adhesive single-sided copper-clad laminate of the present invention was made in the same manner except that the adhesive auxiliary composition obtained in Example 2 was used instead of the adhesive auxiliary composition obtained in Example 1. Got. The film obtained by etching the copper foil had a thickness of 22 μm and a tensile modulus of 4.0 GPa.

Example 5
Following formula (6)

(In formula (6), e, f, and g are average polymerization degrees, respectively, e: f = 75: 25, and a weight average molecular weight is 180,000.) A polyimide precursor represented by N-methyl- After preparing a solution of 15% by weight dissolved in 2-pyrrolidone and applying it on an 18 μm thick electrolytic copper foil (manufactured by Japan Energy Co., Ltd.) using an automatic applicator (manufactured by Yasuda Seiki Seisakusho), the coating thickness is 150 μm. Dry at 130 ° C. for 10 minutes. On the polyimide precursor, after apply | coating the adhesion adjuvant composition obtained in Example 1 by 20 micrometers thickness, it dried at 130 degreeC * 10 minutes. Thereafter, the temperature was raised from 130 ° C. to 350 ° C. in a nitrogen stream over 2 hours, and further imidized by a heat treatment of 350 ° C. × 2 hours to obtain a surface-adhesive single-sided copper-clad laminate of the present invention. The film obtained by etching the copper foil had a thickness of 25 μm and a tensile modulus of 4.5 GPa.

Example 6
In Example 5, the same procedure was used except that the adhesion aid composition obtained in Example 2 was used instead of the adhesion aid composition obtained in Example 1. A laminate was obtained. The film obtained by etching the copper foil had a thickness of 24 μm and a tensile modulus of 4.4 GPa.

Example 7
Using a solution in which the polyimide precursor used in Example 5 was dissolved by 15% by weight in N-methyl-2-pyrrolidone and the same amount of the adhesion aid composition obtained in Example 1 were used. In the same manner as in Example 3, an adhesive single-sided copper-clad laminate of the present invention was obtained. The film obtained by etching the copper foil had a thickness of 20 μm and a tensile modulus of 4.3 GPa.

Example 8
In Example 7, the adhesive single-sided copper-clad laminate of the present invention was made in the same manner except that the adhesive auxiliary composition obtained in Example 2 was used instead of the adhesive auxiliary composition obtained in Example 1. I got a plate. The film obtained by etching the copper foil had a thickness of 21 μm and a tensile modulus of 4.2 GPa.

Example 9
EPPN-501H (triphenylmethane skeleton containing novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 167 g / eq) 50 parts by weight, resin surfaces of the single-sided copper clad laminate obtained in Example 3 -310S (bisphenol A type epoxy resin, Nippon Kayaku Co., Ltd., epoxy equivalent 182 g / eq) 50 parts by weight, Kayahard TPM (Novolac resin having triphenylmethane skeleton, Nippon Kayaku Co., Ltd., hydroxyl group equivalent 97 g / eq ) 54.5 parts by weight, Kayaflex (phenolic hydroxyl group-containing aromatic polyamide-poly (butadiene-acrylonitrile) block copolymer, manufactured by Nippon Kayaku Co., Ltd.), DHT-4A (produced by Kyowa Chemical Industry Co., Ltd.) , Hydrotalcite-based ion scavenger, Mg _4.3 Al ₂ (OH) _12.6 CO ₃ · 3.5 H ₂ O) 5 parts by weight, IXE-100 (manufactured by Toagosei Co., Ltd., a zirconium phosphate ion scavenger) and 2 parts by weight, CS-3N-A (Ube Material Industries, Ltd., purity After bonding with an epoxy adhesive comprising 50 parts by weight of calcium carbonate (purity 99.9% or more), heat-pressure bonding was performed at 170 ° C. and 5 MPa for 60 minutes to obtain a double-sided copper-clad laminate of the present invention.

Example 10
In Example 9, instead of the single-sided copper-clad laminate obtained in Example 3, the double-sided copper-clad laminate of the present invention was prepared in the same manner except that the single-sided copper-clad laminate obtained in Example 4 was used. Obtained.

Example 11
In Example 9, instead of the single-sided copper-clad laminate obtained in Example 3, the double-sided copper-clad laminate of the present invention was prepared in the same manner except that the single-sided copper-clad laminate obtained in Example 5 was used. Obtained.

Example 12
In Example 9, instead of the single-sided copper-clad laminate obtained in Example 3, the double-sided copper-clad laminate of the present invention was prepared in the same manner except that the single-sided copper-clad laminate obtained in Example 6 was used. Obtained.

Example 13
In Example 9, instead of the single-sided copper-clad laminate obtained in Example 3, the double-sided copper-clad laminate of the present invention was prepared in the same manner except that the single-sided copper-clad laminate obtained in Example 7 was used. Obtained.

Example 14
In Example 9, instead of the single-sided copper-clad laminate obtained in Example 3, the double-sided copper-clad laminate of the present invention was prepared in the same manner except that the single-sided copper-clad laminate obtained in Example 8 was used. Obtained.

Comparative Example 1
In Example 5, a single-sided copper-clad laminate (film thickness: 22 μm, tensile elastic modulus: 4.6 GPa) was obtained in the same manner except that the adhesion aid composition of the present invention was not used. A double-sided copper-clad laminate was obtained with a system adhesive.

The results for the peel strengths of the double-sided copper-clad laminates of Examples 9, 10, 11, 12, 13, 14 and Comparative Example 1 are shown in the table.

Table 1
Peel Strength Peel Interface Example 9 10.9 N / cm Copper Foil / Film Example 10 12.6 N / cm Copper Foil / Film Example 11 11.8 N / cm Copper Foil / Film Example 12 11.6 N / cm Copper Foil / Film Example 13 13.3 N / cm Copper Foil / Film Example 14 12.5 N / cm Copper Foil / Film Comparative Example 1 6.3 N / cm Epoxy Adhesive Layer / Film

Claims (9)

An adhesion aid composition containing a phenolic hydroxyl group-containing polyamic acid and a solvent. The phenolic hydroxyl group-containing polyamic acid is represented by the following formula (A)

(In formula (A), R ₁ represents an aromatic group, n is the average number of substituents and represents a positive number of 1 to 4. R ₂ represents a tetravalent aromatic group. X is the average degree of polymerization. The adhesive auxiliary composition according to claim 1, which has a structure represented by: a positive number of 10 to 1,000. The adhesion adjuvant composition of Claim 1 or 2 containing polyimide precursors other than a phenolic hydroxyl group containing polyamic acid. The film obtained by heating the adhesion adjuvant composition of any one of Claims 1-3. The film obtained by apply | coating the adhesion adjuvant composition of any one of Claims 1-3 to a polyimide precursor, and heating. A single-sided copper-clad laminate having the film according to claim 4 or 5. A double-sided copper-clad laminate having the film according to claim 4 or 5. A flexible printed wiring board comprising the film according to claim 4. A multilayer printed wiring board comprising the film according to claim 4.