TWI653291B - Polymer blend composition, flexible metal laminate, and flexible printed circuit board - Google Patents

Abstract

An object of the present invention is to provide a polymer blend composition having excellent adhesion, transparency, and dimensional stability. In particular, it is possible to provide a material that can meet the requirements of fine pitch for further development in the future such as COF applications. The present invention provides a polymer blend composition, which is characterized in that it contains two or more components of polyamidamine and imine resin and satisfies the following conditions (1) and (2). (1) A polyamidoamine imine resin (resin α) containing the general formula (1) and general formula (2) as structural units is taken as an essential component, and the general formula (1) and the general formula ( The molar ratio of 2) is a general formula (1) / general formula (2) = 55/45 to 90/10. (2) A polyimide / imide resin (resin β) having a composition different from that of the resin α containing the general formula (3) as a structural unit is used as an essential component.

Description

Polymer blend composition, flexible metal laminate, and flexible printed circuit board

The present invention relates to a polymer blend composition, and a thin film, a flexible metal laminate, and a flexible printed circuit board using the polymer blend composition. More specifically, it relates to a polymer blend composition, which is excellent in dimensional stability (low warpage, dimensional change), and has both adhesiveness and transparency, and is suitable for use in the field of electrical and electronic equipment. A thin film of the polymer blend composition, a flexible metal laminate, and a flexible printed circuit board.

In the present invention, the "flexible metal laminate" refers to a laminate formed of a metal foil and a thin film layer (resin layer), and is, for example, a laminate useful in the production of a flexible printed circuit board or the like. The "flexible printed circuit board" is, for example, a general term for a so-called flexible circuit board (FPC), a flat cable, a circuit board for tape-and-reel automatic bonding (TAB), or a flip-chip flexible substrate (COF). The flexible metal laminate can be produced by a conventionally known method such as a subtractive method, and can be obtained by partially or completely covering a conductor circuit with a cover film, screen printing ink, or the like, if necessary.

Polyimide resins are widely used as resin films for electronic materials from the viewpoints of excellent heat resistance, chemical resistance, and insulation reliability. However, since polyimide resins are insoluble and infusible, it is necessary to form a thin film by subjecting a solvent-soluble polyimide precursor to a high temperature treatment. As a result, the film is colored, the transparency is reduced, and the workability is poor due to complicated processes, which is a problem. On the other hand, polyimide resins have excellent solubility, can be heat-treated at relatively low temperatures, and can obtain films with excellent transparency, and can be used as a substitute for polyimide resins. Resin films for electronic materials, especially flexible metal laminates for COF.

In the case of a flexible metal laminate for COF, when a driver IC is mounted on a substrate, visible light having a wavelength of 400 to 800 nm is irradiated from the resin film side, and image positioning is performed by a CCD camera or the like for positioning. In particular, resin films are often made of materials with double bonds. At this time, there is a large absorption below 500 nm. Therefore, in general, the wavelength range of 600 to 700 nm is particularly emphasized. Therefore, when the light transmittance of the resin film after the flexible metal laminate is etched is low and the haze is high, the accuracy of the position is reduced, and the density of the wiring pattern and the fineness of the pitch cannot be increased.

In recent years, since the pitch has become finer, the bonding area between the wiring and the resin film has become smaller. Therefore, the bonding strength (peel strength) between the resin film and the metal foil has been required to be higher than in the past. In general, the linear expansion coefficient (CTE) of a resin film is larger than that of a metal. If the difference in CTE is large, the metal laminate will expand and contract due to the heat generated when it is used as an electronic material and cause dimensional changes. . As a result, there is a possibility that the wirings contact each other and cause a short circuit. Moreover, due to the dimensional change, it may be difficult to form a fine-patterned circuit itself. Therefore, it is desirable that the CTE of the metal foil and the resin film be as low as possible. In consideration of the above aspects, various attempts have been made to satisfy high transparency, high adhesion strength, and low CTE.

Patent Document 1 describes that a balance of heat resistance, adhesion, etc. is obtained by coating a copper foil with a high glass transition temperature (Tg) and a low CTE on a copper foil and drying it. Method of metal laminates. However, in Patent Document 1, since a copper foil having a large surface roughness is used, there is a problem that the surface of the resin film after the copper foil is etched becomes rough and visibility is deteriorated due to diffuse reflection of light. In addition, the pattern formability at a narrow pitch is also not good due to the rough surface roughness of the copper foil. Although a copper foil with a large surface roughness also exhibits high adhesion strength, it cannot satisfy both adhesion strength and pattern formability.

Patent Document 2 describes a flexible metal laminated body which is coated with a polyimide precursor resin solution on a copper foil with a low surface roughness and a mirror surface, and is then dried and hardened to provide a copper foil with a metal foil. Polyimide insulation layer composed of multiple layers. However, regarding this metal laminate, the mounting properties of a bare chip and the bonding strength with respect to a copper foil with high gloss or reflectance are insufficient. Furthermore, after the application of the polyimide precursor resin solution, Because it is dried and imidized at high temperature, the processability is poor. Further, since the heat treatment is performed at a high temperature, the copper foil itself recrystallizes, which is not suitable for applications requiring pattern formability in which the pitch is reduced.

Patent Document 3 discloses a technique for improving the adhesion strength by laminating a two-layer polyamidamine / imide resin with a mirror-coated copper foil. [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2008-110612 [Patent Document 2] Japanese Patent Application Publication No. 2007-214555 [Patent Literature 3] Japanese Patent Application Publication No. 2012-11388

[Problems to be Solved by the Invention] However, in Patent Document 3, there are problems in that the steps are complicated due to two laminated layers and the productivity is poor. In addition, since the thickness becomes large, there is a problem in that miniaturization is difficult.

In view of the above-mentioned problems, the present invention aims to provide a polymer blend composition having excellent transparency, adhesion, and dimensional stability by blending a polyamidamine / imine resin having two specific components. Furthermore, a thin film containing the polymer blend composition, a flexible metal laminate, and a flexible printed circuit board are provided. [Means for solving problems]

In order to solve this problem, the results of various studies have been repeated, and it has been found that it can be achieved by the following methods.

That is, this invention consists of the following.

A polymer blend composition characterized in that it contains two or more components of polyamidamine and imine resin and satisfies the following conditions (1) and (2). (1) A polyamidoamine imine resin (resin α) containing the following general formula (1) and general formula (2) as structural units is taken as an essential component, and the general formula (1) and the general formula in resin α The molar ratio of (2) is the general formula (1) / general formula (2) = 55/45 to 90/10. [Chemical 1] General formula (1) General formula (2) (In general formula (1) and general formula (2), R ₁ , R ₂ and R ₃ may be the same or different, and they each represent hydrogen, an alkyl group or alkoxy group having 1 to 4 carbon atoms. (2) A polyamidofluorine imine resin (resin β) containing a general formula (3) as a structural unit and having a composition different from that of the resin α is used as an essential component. [Chemical 3] General formula (3) (In general formula (3), R ₄ and R ₅ may be the same or different, and each represents hydrogen, an alkyl group or an alkoxy group having 1 to 4 carbon atoms.)

The composition ratio of the resin α to the resin β is preferably resin α / resin β = 20/80 to 50/50 by weight. The resin β contains trimellitic anhydride, and is selected from the group consisting of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 3,3', 4,4'-biphenyltetracarboxylic dianhydride. One or more of these groups are preferred as the acid component, and o-toluidine is preferably contained as the amine component.

A thin film containing the polymer blend composition described above, and a flexible metal laminate in which the film is laminated on at least one side of a metal foil.

In the flexible metal laminate, the metal foil has an Rz of 1.2 μm or less and a 60 ° glossiness of 200 or more, and the bonding strength between the metal foil and the film is preferably 7.0 N / cm or more.

In the above flexible metal laminate, the film transmittance of the thin film portion after the metal foil etching at a wavelength of 600 nm is preferably 55% or more, the haze is preferably 20% or less, and the linear expansion coefficient is 10 to 25 ppm / K is preferable, and the film deformation amount at the glass transition temperature in the TMA method is preferably 200 μm or less.

A flexible printed circuit board including the flexible metal laminate. [Effect of the invention]

According to the present invention, a polymer blend composition having excellent adhesiveness, transparency, and dimensional stability, and a film, a flexible metal laminate, and a flexible printed board containing the polymer blend composition can be obtained. In particular, it is possible to obtain materials that can meet the requirements for further refinement of the pitch in the future, such as COF applications.

Hereinafter, the present invention will be described in detail.

(Polymer Blend Composition) The polymer blend composition of the present invention is a composition containing two or more components of polyamidamine and imine resin and satisfying the conditions (1) and (2). It is preferable to mix two or more polyamidoamine imine resins uniformly. For example, two or more polyamidoamine imine resin varnishes which have been dissolved in an organic solvent can be mixed uniformly, and the solvent can be removed And get.

The polyamidofluorine imine resin (α) having a diphenyl ether skeleton and a phenylene skeleton contributes to transparency and adhesion. Moreover, the polyamidofluorine imine resin (β) having a biphenyl skeleton, particularly an o-toluidine skeleton, contributes to dimensional stability (low CTE). In the present invention, a polymer blend composition having excellent transparency, adhesion, and dimensional stability can be obtained by blending these polyamidamine / imide resins.

Generally, polymer blend compositions containing resins containing two or more components have a compatibility ratio with respect to the composition ratios of these components, which are practically compatible with the entire region below the thermal decomposition temperature, and in the entire region. Immiscible immiscible systems and partially miscible systems that are compatible in a specific area. Partially miscible systems are types that cause reactions such as nucleation type and tritium phase decomposition type depending on the conditions of the phase separation state. The homogeneous polymer blend composition in the present invention refers to a state without macroscopic phase separation to such an extent that scattering of visible light does not occur. When macroscopic phase separation occurs, for example, in the case of a thin film, a significant decrease in transparency can be confirmed.

[Condition (1): First component: Resin α] The condition (1) will be described. The condition (1) is a polyamidoamine imine resin (hereinafter also referred to as a resin α) containing the general formula (1) and the general formula (2) as structural units as an essential component. A polyamidamine / imide resin containing a basic structure represented by the general formula (1) and the general formula (2) as a repeating unit is preferred. [Chemical 1] General formula (1) In the general formula (2), in the general formula (1) and the general formula (2), R ₁ , R _2, and R ₃ may be the same or different, and each represents hydrogen, an alkyl group or an alkoxy group having 1 to 4 carbon atoms. The number of carbon atoms is preferably 1 or more and 3 or less, and more preferably 2 or less. R ₁ , R ₂ , and R ₃ are particularly preferably hydrogen.

As for the acid component constituting the resin α, trimellitic anhydride is necessary. Examples of acid components other than trimellitic anhydride include pyromellitic anhydride, phthalic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic anhydride, or 3,3', 4,4'- Biphenyltetracarboxylic anhydride, these can be used alone or in combination of two or more. Among them, pyromellitic anhydride and phthalic anhydride are preferred.

In addition to the above, as far as the acid component is concerned, as long as the purpose of the present invention is not impaired, trimellitic acid, pyromellitic acid, phthalic acid, isophthalic acid, terephthalic acid, Biphenyldicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylarsine dicarboxylic acid, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4,4'-biphenyl Tetracarboxylic acids, 4,4'-dicarboxydiphenyl ether tetracarboxylic acids, bisphenol bis (trimellitic acid esters), naphthalene-2,3,6,7-tetracarboxylic acids, monoanhydrides, dianhydrides, Esterified, or a mixture of two or more may be used.

As the amine component constituting the resin α, 4,4'-diaminodiphenyl ether, p-phenylenediamine, 2,4-diaminotoluene, or the corresponding diisocyanate, etc. must be used alone, or it can be used A mixture of 2 or more types.

Similarly, in addition to the above, as far as the amine component is concerned, as long as the object of the present invention is not impaired, 3,4'-diaminodiphenyl ether, 4,4'-diamino-3,3 'can be used alone. -Dimethyldiphenylmethane, o-toluidine, m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 4,4 ' -Diaminodiphenylhydrazone, 3,3'-diaminodiphenylhydrazone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 2,6- Toluenediamine, 2,4-toluenediamine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Propane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, p-xylylenediamine, m-benzene Dimethylamine, 1,4'-naphthalenediamine, 1,5'-naphthalenediamine, 2,6'-naphthalenediamine, 2,7-naphthalenediamine, 2,2'-bis (4-amine group Phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) ) Benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4 (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] propane, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, etc., or the corresponding diisocyanates, etc., or can be used A mixture of 2 or more types.

In the present invention, it was found that by blending the resin α having the general formula (1) and the general formula (2) and the resin β having the general formula (3), the dimensional stability (low CTE) of the film can be maintained while To improve adhesion and transparency. As the main reason for the improvement of adhesion, it is thought that the ether bond of the general formula (1) imparts flexibility, and the polymer blend composition can easily enter the fine unevenness on the surface even with a mirror metal foil. Therefore, it contributes to the development of the anchor effect and the improvement of the affinity with the metal foil. In addition, the characteristic that the ether bond of the general formula (1) is less likely to undergo thermal degradation contributes to improvement in transparency.

The molar ratio of the general formula (1) and the general formula (2) in the resin α is preferably the general formula (1) / the general formula (2) = 55/45 to 90/10. 60/40 to 85/15 is more preferable, and 65/35 to 80/20 is particularly good. If the molar ratio of the general formula (1) is less than 55, the effect of improving the adhesion and transparency due to the ether bond of the general formula (1) may be insufficient. In addition, when the molar ratio of the general formula (1) exceeds 90, it becomes easy to absorb stress due to thermal history and the like in the manufacturing process due to the soft component, but the resin skeleton becomes excessively soft, and a film is formed instead. It is easy to produce warpage.

The structural unit of the general formula (1) contained in the resin α is preferably 55 mol% or more, more preferably 60 mol% or more, more preferably 65 mol% or more, 90 mol% or less is preferred, and 85 mol%. The following is more preferred, and below 80 mol% is particularly preferred. In addition, the structural unit of the general formula (2) contained in the resin α is preferably 10 mol% or more, more preferably 15 mol% or more, more preferably 20 mol% or more, 45 mol% or less is preferable, and 40 mol. Below ear% is more preferred, below 35 mole% is more preferred. When it is in the said range, the improvement effect of adhesiveness and transparency, and the effect of preventing the curvature at the time of film formation can be expected.

[Condition (2): Second component: Resin β] The condition (2) will be described. The condition (2) is a polyamidamine / imide resin (hereinafter also referred to as a resin β) containing a general formula (3) as a structural unit and having a composition different from that of the resin α as an essential component. Polyamidamine / imide resin containing a basic structure represented by the general formula (3) as a repeating unit is preferred. [Chemical 3] In the general formula (3), R ₄ and R ₅ may be the same or different, and each represents hydrogen, an alkyl group or an alkoxy group having 1 to 4 carbon atoms. The number of carbon atoms is preferably 1 or more and 3 or less, and more preferably 2 or less. Both R ₄ and R ₅ are particularly preferably 1 carbon atom.

The structural unit of the general formula (3) contained in the resin β is preferably 60 mol% or more, more preferably 65 mol% or more, and more preferably 70 mol% or more. The upper limit is not particularly limited, and there is no problem if it is 100 mol%. If it is less than 60 mol%, low CTE characteristics may not be sufficiently developed, and it may be difficult to use it as an insulating material for electrical and electronic equipment such as flexible printed wiring boards.

As for the acid component constituting the resin β, trimellitic anhydride is necessary. Examples of the acid component other than trimellitic anhydride include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, or homobenzene Tetracarboxylic anhydride, these can be used alone or in combination of two or more. Among them, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 3,3', 4,4'-biphenyltetracarboxylic dianhydride are preferred.

As for the acid component, trimellitic acid, pyromellitic acid, phthalic acid, isophthalic acid, terephthalic acid, and biphenyl diphenyl acid can be used alone within a range not impairing the object of the present invention. Carboxylic acid, diphenyl ether dicarboxylic acid, diphenylarsine dicarboxylic acid, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid , 4,4'-dicarboxylic diphenyl ether tetracarboxylic acid, bisphenol bis (trimellitic acid ester), naphthalene-2,3,6,7-tetracarboxylic acid, mono-anhydrides, dianhydrides, esters, etc. Alternatively, a mixture of two or more kinds may be used.

As the amine component constituting the resin β, o-toluidine, 4,4'-diaminobiphenyl, 2,2'-dimethylbiphenyl-4,4'-diamine, and o-anisidine can be used alone. Or these corresponding diisocyanates, etc., or a mixture of two or more kinds may be used.

Similarly, in addition to the above, as far as the amine component is concerned, as long as the object of the present invention is not impaired, 4,4'-diaminodiphenylhydrazone, 3,3'-diaminodiphenylhydrazone, 4 , 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4 '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl- 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl , 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-diethoxy-4,4'-diaminobiphenyl, 4,4'-diamine Benzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, p-phenylenediamine, m-phenylenediamine, 3,3'-diamine Benzamidine aniline, 4,4'-diaminobenzidine aniline, 2,6-toluenediamine, 2,4-toluenediamine, 4,4'-diaminodiphenyl sulfide, 3, 3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylpropane, 3,3 ' Diaminodiphenylpropane, p-xylylenediamine, m-xylylenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine Amine, 2,2'-bis (4-aminophenyloxy) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) ) Phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] propane, 4,4'-bis (4 -Aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, etc., or the corresponding diisocyanate, etc., or a mixture of two or more kinds can be used.

Among the above-mentioned acid component and amine component, a particularly preferable combination is a polyamidamine / imine resin whose main unit is a repeating unit selected and synthesized from the following monomer components.

<Acid component> Trimellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, and 3,3', 4,4'-biphenyltetracarboxylic dianhydride. <Amine component> It is ortho-toluidine, 2, 4-toluenediamine, or the corresponding diisocyanate.

The resin α and the resin β used in the present invention can be synthesized (polymerized) by a usual method. For example, there are an isocyanate method, an osmium chloride method, a low-temperature solution polymerization method, a room temperature solution polymerization method, and the like. From the viewpoint of manufacturing cost, an isocyanate method in which a polymer varnish is obtained by a decarboxylation reaction is particularly preferable.

Examples of the solvent used in the polymerization include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, and 1,3- Ethylamine solvents such as dimethyl-2-imidazolidone; Sulfur solvents such as dimethylmethylene and cyclobutane; Ketone solvents such as cyclohexanone and methyl ethyl ketone; Nitro such as nitrobenzene and nitroethane Ether solvents such as diethylene glycol dimethyl ether and tetrahydrofuran; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as γ-butyrolactone and γ-valerolactone, etc., can be used alone or as a mixture Use of solvents.

The composition ratio of the resin α and the resin β is preferably resin α / resin β = 20/80 to 50/50 (weight ratio). 25/75 ～ 40/60 (weight ratio) is better. If the resin α is too large (more than 50 (weight ratio)), the low CTE characteristics of the resin β may not be fully exhibited, and it may be difficult to use it as an insulating material for electrical and electronic equipment such as flexible printed wiring boards. tendency. On the other hand, if the resin α is too small (less than 20 (weight ratio)), the characteristics of the resin α, in particular, characteristics such as adhesion strength and transparency, may not be exhibited.

The content of the resin α in the polymer blend composition of the present invention is preferably 10 to 50% by weight, more preferably 15 to 50% by weight, and 20 to 50% by weight relative to the total weight of the polymer blend composition. % Is better. When the content of the resin α exceeds 50% by weight, the CTE tends to be high, and it tends to become difficult to use it as an insulating material for electrical and electronic equipment such as a flexible printed wiring board. If the content of the resin α is less than 10% by weight, the characteristics inherent in the polymer containing the structure represented by the general formula (1), such as characteristics such as adhesion strength and transparency, tend not to be maintained.

The polymer blend composition of the present invention is directly laminated on a metal foil having a ten-point average roughness (Rz) of 1.2 μm or less and a 60 ° gloss of 200 or more without an adhesive, according to IPC-FC241 ( IPC-TM-650, 2.4.9 (A)) and a metal foil and a polymer blend composition layer (thin film layer) when a circuit pattern is formed by a subtractive method are preferably 7.0N / cm or more.

<Polyfluorene-imide resin solution> The molecular weights of the polyamine-imide resin α and the resin β are equivalent to those in N-methyl-2-pyrrolidone (polymer concentration 0.5 g / dl), A molecular weight with a logarithmic viscosity of 0.1 to 2.8 dl / g at 30 ° C is preferred, and a molecular weight equivalent to 0.3 to 2.5 dl / g is more preferred. If the logarithmic viscosity is less than 0.1 dl / g, the mechanical properties may be insufficient when forming a molded article such as a thin film. If it exceeds 2.8 dl / g, the solution viscosity may increase and the forming process may become difficult. In terms of proper solution viscosity, the B-type viscosity at 25 ° C is in the range of 50 to 1000 dPa · s. When the viscosity is out of the above range, the coatability may decrease.

The concentration of the polyamidoamine imine resin α and the resin β solution (polymer blend composition solution) can be selected in a wide range, but is generally about 5 to 40% by weight, preferably 8 to 30% by weight Left and right are better. If the concentration is out of the above range, there is a concern that drying efficiency is deteriorated, formation of a smooth surface becomes difficult, and necessary heat is increased. As the preferred solvent for the polyamidoamine imine resin solution, considering the coating properties and the like, in terms of the diluted solvent after polymerization, it is preferably N, N-dimethylformamide, 1,3-dimethyl -2-imidazolidone, tetramethylurea, cyclobutane, dimethylmethylene, γ-butyrolactone, cyclohexanone, cyclopentanone, etc., N, N-dimethylacetamide, N- Methyl-2-pyrrolidone is particularly preferred. In addition, one part of these may be replaced with hydrocarbon organic solvents such as toluene and xylene; ether organic solvents such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetrahydrofuran; methyl ethyl ketone, methyl isobutyl Ketone organic solvents such as ketones. Moreover, since these solvents can also be used as a solvent at the time of a polymerization, the resin solution excellent in processability can be obtained easily considering the point which can apply | coat a polymerization solution as it is.

If necessary, in order to improve various characteristics of the flexible metal laminate or the flexible printed circuit board, for example, mechanical characteristics, electrical characteristics, smoothness, flame retardance, etc., the polymer blend of the present invention may be composed. It is used by mixing or reacting with other resins, organic compounds, and inorganic compounds. For example, a lubricant (silica, talc, silicone, etc.), an accelerator, or a flame retardant (phosphorus or System, aluminum hydroxide, etc.), stabilizers (antioxidants, UV absorbers, polymerization inhibitors, etc.), plating activators, organic or inorganic fillers (talc, titanium oxide, silicon dioxide, fluorine polymer microparticles) , Pigments, dyes, calcium carbide, etc.); others such as silicone compounds, fluorine compounds, isocyanate compounds, blocked isocyanate compounds, acrylic resins, urethane resins, polyester resins, polyamide resins, epoxy resins, phenolics Resins and organic compounds such as resins; or such hardeners; inorganic compounds such as silicon oxide, titanium oxide, calcium carbonate, and iron oxide. Moreover, if necessary, a polyimidization catalyst such as an aliphatic tertiary amine, an aromatic tertiary amine, a heterocyclic tertiary amine, an aliphatic acid anhydride, an aromatic acid anhydride, or a hydroxy compound may be added. For example, triethylamine, triethylenediamine, dimethylaniline, pyridine, methylpyridine, isoquinoline, imidazole, undecene, hydroxyacetophenone, etc. are preferred, and pyridine compounds, imidazole compounds, undecene Particularly preferred compounds are among them benzimidazole, triazole, 4-pyridinemethanol, 2-hydroxypyridine, diazabicyclo [5.4.0] undec-7-ene, 2-hydroxypyridine, diazabicyclo [5.4.0] Eleven-7-ene is more preferred.

<Film> The film of the present invention is a film containing a polymer blend composition, and can be produced using the polymer blend composition solution (varnish). The polymer blend composition solution (varnish) is applied to a support such as a metal foil, an endless belt, a drum, a carrier film, and the coating film is dried. The film is peeled from the support as appropriate, and then heat-treated. And formed.

(Coating) A method for applying the polymer blend composition to a support such as a metal foil may be a conventionally known method. For example, a roll coater, a knife coater, a blade coater, or a gravure coater may be used. , Die coater, reverse coater, etc.

(Drying) The drying conditions after the polymer blend composition solution is cast are not particularly limited, and generally, the boiling point (Tb (° C)) of the solvent used for the polymer blend composition solution is lower than 70 After the initial drying is performed at a temperature of -130 ° C, it is preferable to further perform secondary drying (heat treatment) at a temperature near or above the boiling point of the solvent. If the initial drying temperature is higher than (Tb-70) ° C, the coating surface will be foamed, and the non-uniformity of the residual solvent in the thickness direction of the resin layer (polymer blend composition layer) will increase, resulting in film relaxation. Case. Moreover, the flexible metal laminated body laminated | stacked with this film may generate | occur | produce a curvature (curl), and the curvature of the flexible printed circuit board obtained by circuit processing may also become large. When the drying temperature is lower than (Tb-130) ° C, the drying time may be prolonged and the productivity may be reduced. The initial drying temperature varies depending on the type of solvent, but is generally about 60 to 150 ° C, preferably about 80 to 120 ° C. The time required for the initial drying is generally an effective time under the above-mentioned temperature conditions, as long as the residual solvent ratio in the coating film is about 5 to 40% by weight, generally about 1 to 30 minutes, and about 2 to 15 minutes. good.

The secondary drying (heat treatment) conditions may be performed at a temperature near or above the boiling point of the solvent, and generally 150 to 500 ° C, preferably 200 to 400 ° C. If the secondary drying temperature is low, the drying time may be prolonged and productivity may be reduced. If it is too high, depending on the resin composition, a degradation reaction may occur, the resin film may become brittle, and the cost may increase. The time required for the secondary drying is generally an effective time in which the residual amount of the solvent in the coating film becomes 1% by weight or less under the above-mentioned temperature conditions, and is generally several minutes to several tens of minutes.

In the present invention, the initial drying and the secondary drying may be performed in an inert gas environment or under reduced pressure. Examples of the inert gas include nitrogen, carbon dioxide, helium, argon, and the like, and it is preferable to use nitrogen that is easily available. In addition, when it is performed under reduced pressure, it is preferably performed at a pressure of about 10 ^-5 to 10 ³ Pa, and more preferably about 10 ^-1 to 200 Pa.

In the present invention, the method of initial drying and heat treatment is not particularly limited, and it can be performed by a conventionally known method such as a roll support method or a floating method. In addition, continuous heat treatment may be performed using a heating furnace such as a tenter type.

The film containing the polymer blend composition of the present invention obtained in this way can obtain high-strength, high-elongation, and tough films without impairing the low CTE properties of the resin β, and having excellent mechanical properties.

In addition, the thickness of the film can be selected in a wide range. Generally, the thickness of the film after being completely dried is about 5 to 100 μm, and preferably about 10 to 50 μm. If the thickness is less than 5 μm, mechanical properties such as film strength and operability may be deteriorated. On the other hand, if the thickness is more than 100 μm, characteristics such as flexibility and processability (drying, coating properties) may be obtained. ) And so on.

Moreover, you may perform surface treatment as needed. For example, surface treatments such as hydrolysis, corona discharge, low-temperature plasma, physical roughening, and easy coating treatment can be performed.

<Flexible metal laminate> The flexible metal laminate of the present invention is preferably a two-layer metal laminate in which the above-mentioned film and metal foil are directly laminated without interposing an adhesive. Examples of the manufacturing method include a lamination method and a casting method, which are not particularly limited, and it is preferable to use a casting method that is excellent in processability and can be manufactured inexpensively.

The thickness of the metal foil is not particularly limited, and a metal foil of 1 to 50 μm can be suitably used, preferably 3 to 35 μm, and more preferably 3 to 18 μm. If the thickness of the metal foil is less than 1 μm, the productivity during transportation may be reduced, and if it is more than 50 μm, the looseness and winding properties of the elongated object may be poor, and the productivity may be reduced.

A metal foil having a ten-point average roughness Rz of 1.2 μm or less can be suitably used, preferably 1.0 μm or less, and more preferably 0.8 μm or less. If Rz exceeds 1.2 μm, the unevenness of the copper foil may be transferred to the resin film, the transparency of the resin film after etching may be reduced, and sufficient positioning accuracy may not be secured.

The gloss of the metal foil is 200 or more, 300 or more is preferable, and 400 or more is more preferable. Gloss is measured in accordance with JIS-Z8741-1997, and is irradiated at an incident angle of 60 °, and the reflected light at 60 ° is measured. The higher the gloss, the lower the surface roughness and the less fluctuations that are not reflected in the surface roughness, so the surface becomes smoother. Therefore, the higher the gloss, the better, but it is sufficient if it is about 800.

The flexible metal laminate of the present invention is preferably formed by directly coating a solution of the polymer blend composition with a metal foil, drying the coating film, and performing heat treatment as appropriate. As the metal foil, copper foil, aluminum foil, steel foil, nickel foil, etc. can be used; composite metal foils of these composites, zinc, chromium, nickel, cobalt, molybdenum compounds, or alloys thereof can be used. Metal foil processed. A more preferred metal foil is copper foil, but as long as the above characteristics are satisfied, a commercially available electrolytic foil or rolled foil can be used as it is. For example, "SV", "RCF" made by Fukuda Metal Foil Industry Co., Ltd., "GHY" made by Nissho Metals Co., Ltd., or "TQ-M4-VSP" made by Mitsui Metals Mining Co., Ltd. Wait.

In the present invention, the amount of deformation refers to the amount of change in the thin film due to the release of internal stress when the flexible metal laminate is exposed to a temperature above the glass transition temperature, and the amount of deformation is preferably 200 μm or less. If it exceeds 200 μm, the amount of change becomes large, the size change of the flexible metal laminate becomes large, and the position accuracy at the time of mounting may be insufficient.

The flexible metal laminate of the present invention obtained in this way can be obtained without impairing the high transparency, high adhesive strength, and low CTE of resin β, and the mechanical properties of its insulating resin layer. Excellent, that is, a flexible metal laminate in which a high-strength, high-elongation, and tough film is laminated.

The adhesion strength between the metal foil and the film in the flexible metal laminate is preferably 7.0 N / cm or more, more preferably 7.5 N / cm or more, and even more preferably 8.0 N / cm or more. If it is less than 7.0 N / cm, the heat generated during use as an electronic component repeatedly shrinks and expands, and there is a possibility that the wiring may be peeled from the substrate, and it may become difficult to make the pitch finer. Therefore, the higher the bonding strength, the better, but it is sufficient if it is 10.0 N / cm or more.

In the present invention, the light transmittance is a characteristic related to the positioning accuracy when the driver is installed, and a parallel light transmittance of 600 nm is taken as the light transmittance. The light transmittance of the thin film portion after the metal foil of the flexible metal laminate is etched is preferably 60% or more, more preferably 65% or more, and even more preferably 70% or more. If it is less than 60%, the positioning accuracy at the time of installation may be lowered, and it may become difficult to reduce the pitch.

In the present invention, haze and light transmittance are also characteristics related to positioning accuracy. Haze is an index of turbidity. The higher the haze, the lower the transparency of the object, which corresponds to the lower the transmittance. The haze of the thin film portion after the metal foil of the flexible metal laminate is etched is preferably 20% or less, more preferably 15% or less, and even more preferably 13% or less.

The linear expansion coefficient (CTE) of the thin film portion after the metal foil of the flexible metal laminate is etched is preferably 10 to 25 ppm / K, more preferably 12 to 25 ppm / K, and even more preferably 15 to 25 ppm / K. [Industrial availability]

The flexible metal laminate of the present invention has excellent transparency because of the surface characteristics of the copper foil. Furthermore, it has excellent adhesion by blending two types of polyamidamine / imine resins with a specified resin composition, and it has excellent dimensional stability and processability due to a specific blend ratio. Therefore, as an electronic material, it is not only used for FPC, flat cable, and TAB applications, but also suitable for use in COF film carrier tapes with high demand for miniaturization and high performance, and miniaturization of wiring pitch. [Example]

Hereinafter, the present invention will be described in more detail through experimental examples. The present invention is not limited to experimental examples.

<Logarithmic Viscosity> The polyamidamine / imine resin samples (resin α, resin β) obtained in the experimental example were dissolved in N-methyl-2-pyrrolidone to obtain a polymer concentration of 0.5 g / dl. The solution viscosity and solvent viscosity of the solution were measured at 30 ° C using an Ubbelohde-type viscosity tube, and calculated according to the following formula. Logarithmic viscosity (dl / g) = [ln (V1 / V2)] / V3 In the formula, V1 represents the solution viscosity measured using an Ubbelohde-type viscosity tube, and V2 represents the solvent viscosity measured using an Ubbelohde-type viscosity tube. V1 and V2 are obtained from the time when the polymer solution and the solvent (N-methyl-2-pyrrolidone) pass through the capillary tube of the viscosity tube. V3 is the polymer concentration (g / dl).

<Polymer Concentration> Using the polyamidamine / imine resin samples (Resin α, Resin β) obtained in the experimental example, weighing (W1) was performed so that the weight of the polymer resin solution was 0.20 g, and hot air was applied at 240 ° C. After drying in a dryer for 1 hour, the weight (W2) was measured again, and the polymer concentration was calculated from the amount of the polymer remaining without volatilization. Polymer concentration (% by weight) = (W2 / W1) × 100

<Etching> A polyimide / imide resin sample (resin α, resin β) obtained in the experimental example was applied to a metal foil, and after drying, it was immersed in a 35% iron (III) chloride aqueous solution, and the metal foil was It is completely removed (etched) to obtain a single-layered etched film.

<Glass Transition Temperature and Deformation> The TMA (thermo-mechanical analyzer / manufactured by Seiko Instruments Inc.) tensile load method was used for measurement under the following conditions. The glass transition temperature is defined as the intersection of the baseline before the endothermic peak and the tangent to the endothermic peak in the endothermic curve at the time of temperature rise. The amount of deformation is calculated from the change in length of the inflection point of the baseline and the endothermic peak point. As the sample, a thin film portion obtained by etching the metal foil of the flexible metal laminate obtained in the experimental example was used. Load: 5g Sample size: 4 (width) × 20 (length) mm Heating rate: 10 ° C / min Environment: nitrogen

<Linear expansion coefficient (CTE)> The measurement was performed under the following conditions using a TMA (Thermo-mechanical Analyzer / Seiko Instruments Inc.) according to the tensile load method. As the sample, a thin film portion obtained by etching the metal foil of the flexible metal laminate obtained in the experimental example was used. CTE is calculated from the average value of 100 to 200 ° C. The lower the CTE, the higher the dimensional stability. Load: 5g Sample size: 4 (width) × 20 (length) mm Heating rate: 10 ° C / min Environment: nitrogen

<Glossiness> The glossiness of the metal foil is measured according to the specular glossiness measurement method described in JIS Z8741-1997. The light source is irradiated at an incident angle of 60 °, and the intensity of light reflected at a reflection angle of 60 ° is measured. The reflection angle here refers to a direction perpendicular to the light irradiation surface as 0 °. The measuring instrument used a VG200 gloss meter of Japan Denshoku Corporation. The measurement is performed on the resin-coated surface of the metal foil.

<Adhesive strength> The flexible metal laminate sample obtained in the experimental example was made into a circuit pattern by a subtractive method in accordance with IPC-FC241 (IPC-TM-650, 2.4.9 (A)), and the metal foil and the Adhesive strength of the film (polymer blend composition layer).

<Light transmittance> Using a thin film portion obtained by etching the metal foil of the flexible metal laminate obtained in the experimental example, the measurement was performed using a Japanese spectrophotometer V650 spectrophotometer. In order to measure the parallel light transmittance, the measurement is performed in a standard state without using an integrating sphere unit that receives diffused light. Measurement range: 300 to 800 nm, and a value read at 600 nm.

<Haze> Using a thin film portion obtained by etching the metal foil of the flexible metal laminate obtained in the experimental example, the measuring instrument was measured using NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. and measured in accordance with JIS-K7136. The value of the scattered light transmittance divided by the total light transmittance is expressed as a percentage.

<Blending> The resin α and / or the resin β are added so that the polymer concentration becomes the value described in Table 1. Using dimethylacetamide as a diluting solvent, stir in a 100 ° C. oil bath for 2 hours until homogeneous, and cool to room temperature to obtain a polymer blend composition. When not blended, it was diluted with dimethylacetamide to the polymer concentration described in Table 1.

(Synthesis Example 1 (Resin α)) Trimellitic anhydride (86 mol%, 86.46 g), pyromellitic anhydride (7 mol%, 10.91 g), 4,4'-diisocyanate diphenyl ether (75 mol %, 93.64g), 1,4-benzenediisocyanate (25 mole%, 19.82g), diazabicyclo [5.4.0] undec-7-ene (0.76g) added N-methyl-2- Pyrrolidone (390.24 g) was added to a separable flask at a polymer concentration of 30% by weight. After reacting in a 100 ° C oil bath for 5 hours, phthalic anhydride (7 mole%, 7.41 g) was added, and after stirring for 1 hour, N-methyl-2-pyrrolidone (291.09 g) was added and diluted to The polymer concentration was 20% by weight, and after cooling to room temperature, a polyamidoamine imine resin (α-1) was obtained.

(Synthesis Example 2) Trimellitic anhydride (100 mole%, 76.85g), diphenylmethane diisocyanate (100 mole%, 99.10g), diazabicyclo [5.4.0] undec-7-ene (0.61 g) N-methyl-2-pyrrolidone (564.38 g) was added, and it was added to a separable flask at a polymer concentration of 20% by weight. After reacting in a 100 ° C. oil bath for 5 hours, N-methyl-2-pyrrolidone (235.16 g) was added, diluted to a polymer concentration of 15% by weight, and cooled to room temperature to obtain a polyamidamine imine resin.

(Synthesis Example 3 (Resin β)) Trimellitic anhydride (80 mole%, 41.50g), 3,3 ', 4,4'-benzophenonetetracarboxylic acid (12.5 mole%, 10.88g), 3, 3 ', 4,4'-biphenyltetracarboxylic acid (7.5 mole%, 5.96g), o-toluidine diisocyanate (100 mole%, 71.36), diazabicyclo [5.4.0] 7-ene (0.21 g) was charged with N-methyl-2-pyrrolidone (600.24 g), and it was added to a separable flask at a polymer concentration of 15% by weight. After reacting in a 100 ° C. oil bath for 5 hours, it was cooled to room temperature to obtain a polyamidofluorine imine resin (β-1).

(Synthesis Example 4 (Resin β)) Trimellitic anhydride (100 mole%), o-toluidine diisocyanate (80 mole%), and toluene diisocyanate (20 mole%) were used under the same conditions as in Synthesis Example 3 This was carried out to obtain a resin (β-2).

(Experimental Examples 1 to 6) A polymer blend composition obtained by changing the blending ratio of resin α as shown in Tables 1 and 2 was applied to an electrolytic copper foil (trade name "CF- "T9DA-SV": manufactured by Fukuda Metal Foil Powder Co., Ltd .: Rz = 0.75 μm, gloss = 500), and dried at 90 ° C for 8 minutes at the initial stage. Then, it fully dried under vacuum until the solvent evaporated, and the metal laminated body was obtained. By increasing the blending ratio of the resin α, it is possible to confirm that the adhesion strength is improved, and that the transmittance is improved and the haze is reduced. It can be seen that the presence of the resin α is indispensable in the present invention. As the blending ratio of the resin α increases, the linear expansion coefficient also increases. As the blending ratio becomes higher, the deviation from the linear expansion coefficient of copper becomes larger. Therefore, it is known that the control of the blending ratio is also important.

(Experimental Example 7) A metal laminate was obtained under the same conditions as in Experimental Example 1 except that the resin composition of resin α was changed as shown in Tables 1 and 2. By changing the composition of the resin α, the characteristics of the metal laminate are significantly deteriorated. From this, it can be understood that the composition system of the resin α is important in the present invention.

(Experimental Examples 8 and 9) A metal laminate was obtained under the same conditions as in Experimental Example 1 except that the blending ratio of resin α alone was changed as shown in Tables 1 and 2. When the resin α was contained alone, it was confirmed that the linear expansion coefficient was insufficient. From this, it is understood that the presence of the resin β is important in the present invention.

(Experimental Examples 10 to 13) A metal laminate was obtained under the same conditions as in Experimental Example 1 except that the composition of the resin β and the blending ratio were changed as shown in Tables 1 and 2. As in Experimental Example 1, improvement in adhesion strength, light transmittance, and haze due to the blending of the resin α was confirmed. From this, it is understood that the presence of the resin α is important in the present invention.

(Experimental Example 14) Except for changing to copper foil as shown in Table 2 (trade name "CF-T4X-SV": manufactured by Fukuda Metal Foil Powder Co., Ltd .: Rz = 1.28 μm, gloss = 90), A metal laminate was obtained under the same conditions as in Experimental Example 1. By increasing the surface roughness Rz of the copper foil and decreasing the gloss, although the adhesion strength was improved, the transmittance and haze were also significantly deteriorated. From this, it turns out that the copper foil characteristic is important in this invention.

【Table 1】 TMA: trimellitic anhydride, BTDA: 3,3 ', 4,4'-benzophenonetetracarboxylic acid, BPDA: 3,3', 4,4'-biphenyltetracarboxylic acid PMDA: pyromellitic anhydride, FDA : Phthalic anhydride, TODI: o-toluidine diisocyanate, TDI: toluene diisocyanate MDI: diphenylmethane diisocyanate, DFEDI: 4,4'-diisocyanate diphenyl ether, FDI: 1,4-benzene Diisocyanate

【Table 2】

Claims (11)

A polymer blend composition, characterized in that it contains polyamidoamine imine resin with more than two components, and satisfies the following conditions (1) and (2); (1) it will contain the following general formula (1) and Polyamine-imide resin (resin α) as a structural unit of the general formula (2) is taken as an essential component, and the molar ratio of the general formula (1) to the general formula (2) in the resin α is the general formula (1) ) / General formula (2) = 55/45 ～ 90/10; General formula (1) In the general formula (2), in the general formula (1) and the general formula (2), R ₁ , R ₂ and R ₃ may be the same or different, and each represents hydrogen, an alkyl group or alkoxy group having 1 to 4 carbon atoms; (2) A polyamidamine / imine resin (resin β) having a composition different from that of the resin α containing the following general formula (3) as a structural unit is taken as an essential component; In the general formula (3), R ₄ and R ₅ may be the same or different, and each represents hydrogen, an alkyl group or an alkoxy group having 1 to 4 carbon atoms. For example, the polymer blend composition of the first patent application range, wherein the composition ratio of the resin α to the resin β is a resin α / resin β = 20 / 80-50 / 50 weight ratio. For example, the polymer blend composition of claim 1 or 2, wherein the resin β contains trimellitic anhydride, and is selected from the group consisting of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride One or more of the group consisting of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride are acid components, and o-toluidine is included as an amine component. A film containing a polymer blend composition as set forth in any one of claims 1 to 3 of the scope of patent application. A flexible metal laminated body is directly laminated on at least one side of a metal foil with a film such as the item 4 in the scope of patent application. For example, the flexible metal laminate according to item 5 of the patent application, wherein the Rz of the metal foil is 1.2 μm or less, the gloss at 60 ° is 200 or more, and the bonding strength between the metal foil and the film is 7.0 N / cm the above. For example, the flexible metal laminate according to item 5 or 6 of the patent application scope, wherein the light transmittance of the film portion after the metal foil is etched at a wavelength of 600 nm is 55% or more. For example, the flexible metal laminate of the scope of application for the patent No. 5 or 6, wherein the haze of the thin film portion after the metal foil is etched is 20% or less. For example, the flexible metal laminated body in the scope of application for the patent No. 5 or 6, wherein the linear expansion coefficient of the thin film portion after the metal foil is etched is 10 to 25 ppm / K. For example, the flexible metal laminate according to item 5 or 6 of the patent application scope, wherein the amount of film deformation at the glass transition temperature in the TMA method of the thin film portion after the metal foil is etched is 200 μm or less. A flexible printed circuit board includes a flexible metal laminate according to any one of claims 5 to 10.