JP5152028B2 - Polymer blend composition, film, and metal laminate - Google Patents

Description

The present invention relates to a polymer blend composition, and a film and a metal laminate using the polymer blend composition. More specifically, the present invention relates to adhesive and mechanical properties used in the fields of electrical and electronic equipment such as flexible printed boards. It relates to an improved insulating material.
Here, the “metal laminate” is a laminate formed from a metal foil and a resin layer, and is, for example, a laminate useful for producing a flexible printed circuit board or the like. In addition, the “flexible printed circuit board” can be manufactured by a conventionally known method such as a subtractive method using a metal laminate, for example, and a conductor circuit may be partially or entirely covered with a coverlay film, A so-called flexible circuit board (FPC), flat cable, circuit board for tape automated bonding (TAB), chip-on-flexible board (COF), and the like, which are covered with screen printing ink or the like, are generically named.

Polyimide resins and polyamideimide resins are widely used as insulating materials for electric and electronic devices because they are excellent in heat resistance, chemical resistance, and insulation reliability. Among them, the polyamideimide resin having an O-tolidine skeleton as a biphenyl skeleton described in Patent Document 1 has a low coefficient of thermal expansion (CTE) and a coefficient of humidity expansion (CHE), and is excellent in electrical insulation and heat resistance. Therefore, it is known that it is useful as a metal laminate for flexible printed wiring boards.
However, polyamideimides having these O-tolidine skeletons have a high productivity, such as normal drying conditions and processing conditions, especially short-time heat treatment at high temperatures, due to their rigidity in solution molding methods such as casting. Under high drying and processing conditions, the resulting film is whitened and easily embrittled, and mechanical properties such as strength, elongation and elastic modulus are difficult to express as expected from its molecular structure. there were. For the same reason, the adhesiveness with adhesives used in the electrical and electronic equipment fields has not been sufficient. For example, when used as an insulating substrate of a flexible printed wiring board, there is a problem in adhesion with an adhesive for attaching a reinforcing plate, and when a metal laminate itself for a flexible printed wiring board is molded. In addition, in the so-called laminating method in which the polyamideimide film and the metal foil are bonded with an adhesive, the adhesion between the polyamideimide film and the adhesive is insufficient, and the metal layer is deposited on the polyamideimide film by a metalizing method or the like. In the manufacturing method to laminate | stack, there existed a problem that a metal laminated body with large adhesive strength was not obtained.
In general, various attempts have been made to improve the adhesion. For example, Patent Document 2 discloses a technique for improving the adhesiveness between a film and a metal layer by a plasma discharge processing technique, and Patent Document 3 discloses a sputtering technique and conditions. However, in the discharge treatment, the effect of improving the adhesiveness, in particular, the maintenance of the adhesiveness after passing through various processes is not sufficient, and the addition of a metallic compound reduces the electrical insulation, and also in the sputtering technique. There was a problem in maintaining the adhesiveness after the steps such as heat treatment.
In addition, these technologies have a problem that productivity is low.

JP 2001-105530 A JP-A-2-134241 Japanese Patent Laid-Open No. 2-98994

As a result of intensive studies to achieve the above object, the present inventors have found that the cause of the whitening and embrittlement of the polyimide resin having a biphenyl skeleton, particularly the polyamide-imide resin having an O-tolidine skeleton, is irregular. By identifying the crystalline structure and blending two or more components of polyimide resin and controlling the crystallinity, the characteristics such as low CTE and low CHE of the O-tolidine skeleton and biphenyl skeleton were maintained. As such, the inventors succeeded in developing a composition, a film, and a metal laminate having improved mechanical properties and adhesion.
Here, the polyimide resin refers to a resin having an imide bond in a molecular chain, for example, a polyimide resin or a polyamideimide resin.

(1)
A polymer blend composition comprising a mixture of two or more components of a polyimide resin and the following (a) to (c) :
(A) One component of the polyimide resin to be mixed is a polyimide resin (resin α) containing the following general formula (1) as a structural unit;
(In general formula (1), R1 and R2 may be the same or different, and each represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group.)
(B) One component of the polyimide resin to be mixed is a polyimide resin (resin β) having a composition different from that of the resin α, and includes the following general formula (2) and / or general formula (3) as a structural unit. about;
(In the general formula (2), R3 and R4 may be the same or different and each represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group. X represents a direct bond, —SO ₂ — , -O-, or -CH _2- .)
(In the general formula (3), X represents a direct bond, —SO ₂ —, —O—, or —CH ₂ —. In the general formula (2) and general formula (3), X may be different from each other. good.)
(C) The weight ratio of the resin α and the resin β is resin α / resin β = 90/10 to 20/80.
(2)
The ratio of the general formula (1) in the resin α is 50 mol% or more when the total amine component is 100 mol%, and
When the total amine component and the total acid component in the resin β are 200 mol%, the structural unit of the general formula (2) and / or the general formula (3) is included in an amount of 50 mol% or more.
The polymer blend composition as described in (1) above.
(3)
Resin α contains trimellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride as an acid component, and 3,3′-dimethyl-4,4′-diaminobiphenyl or 3,3 as an amine component The polymer blend composition according to (1) or (2), which is a polyamide-imide resin containing 3′-dimethyl-4,4′-diisocyanatobiphenyl.
(4)
The polymer blend according to any one of (1) to (3), wherein the resin β is a polyimide resin containing 3,3′-4,4′-diphenylsulfonetetracarboxylic dianhydride as an acid component Composition.
(5)
Resin β contains 3,3′-4,4′-diphenylsulfonetetracarboxylic dianhydride as an acid component, and 3,3′-dimethyl-4,4′-diaminobiphenyl or 3,3 ′ as an amine component The polymer blend composition as described in any one of (1) to (4), which is a polyimide resin containing dimethyl-4,4′-diisocyanate biphenyl.
(6)
Resin β contains trimellitic anhydride as the acid component, and as the amine component, diaminodiphenylsulfone or diphenylsulfone diisocyanate, diaminodiphenylmethane or diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diaminobiphenyl or 3, (1) to (3) characterized by being a polyamide-imide resin characterized by containing at least one member of the group of 3'-dimethyl-4,4'-diisocyanate biphenyl and diaminodiphenyl ether or diphenyl ether diisocyanate. ) A polymer blend composition according to any one of the above.
(7)
The film which consists of a polymer blend composition in any one of (1)-(6).
(8)
The fime which has at least 1 layer which consists of a film as described in (7).
(9)
A metal laminate in which the film according to (7) or (8) is laminated directly on at least one side of a metal foil or via an anchor layer.
(10)
The anchor layer contains trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and pyro The metal laminate according to (9), comprising merit acid anhydride and containing 1,5-naphthalenediamine or 1,5-naphthalene diisocyanate as an amine component.

  According to the present invention, a polymer blend composition, a film, and a metal laminate are obtained which are excellent in mechanical properties and adhesiveness with an adhesive used in the field of electrical and electronic fields.

  In particular, while maintaining the properties of the polyimide resin and polyamideimide resin having the structure of the general formula (1) such as an O-tolidine skeleton excellent in low CTE, low CHE, etc., they are used in the mechanical properties and electrical and electronic fields. Since a polymer blend composition, a film, and a metal laminate having improved adhesion with an adhesive or the like can be obtained with high productivity, it is industrially useful.

XRD analysis result of Comparative Example 1 by XRD transmission method

  Hereinafter, embodiments of the polymer blend composition, film, and metal laminate of the present invention will be described.

<Polymer blend composition>
The polymer blend composition of the present invention is a polymer blend composition characterized in that two or more components of a polyimide resin (polyimide resin, polyamideimide resin) are uniformly mixed, for example, dissolved in an organic solvent. Two or more kinds of polyimide resin varnishes (polyimide varnish and / or polyamideimide varnish) are uniformly mixed, and the solvent is removed. For example, in the case of two components, it may be a blend of polyimide resin and polyimide resin, a blend of polyimide resin and polyamideimide resin, or a blend of polyamideimide resin and polyamideimide resin. Also good.
Usually, polymer blends composed of two or more polymer compositions are compatible with these composition ratios in a compatible system in all practical areas below the thermal decomposition temperature, and incompatible in all areas. There are compatible systems and partial compatible systems that are compatible in a certain region. There are types of partial compatible systems that induce reactions such as nucleation type and spinodal decomposition type depending on the conditions of the phase separation state. In the invention, the uniform polymer blend composition refers to a state where there is no macro phase separation to the extent that scattering by visible light does not occur. When macro phase separation occurs, for example, in the case of a film, a significant decrease in transparency is confirmed.
In the present invention, in a polymer blend composition in which two or more component polyimide resins are mixed, at least one of them is a polyimide resin (resin) containing the following general formula (1) as a structural unit A polymer blend composition comprising α).
In the polymer blend composition of the present invention, the content of the resin α is preferably 1 to 99 weight percent, more preferably 20 to 90 weight percent, still more preferably 30 to 70 weight percent based on the total weight of the polymer blend composition. Weight percent.
If the content of the resin α exceeds 99 weight percent, whitening and embrittlement due to the polymer structure including the structure represented by the general formula (1) is likely to occur during molding into a film and the like, and its mechanical properties There is a tendency that the effect of improving adhesiveness is small. If the content of the resin α is less than 1 percent by weight, the characteristics inherently possessed by the polymer including the structure represented by the general formula (1), particularly characteristics such as low CTE and low CHE tend not to be maintained. Further, the ratio of the general formula (1) in the resin α component is preferably 50 mol% or more, more preferably 70 mol% or more when the total amine component is 100 mol%. The upper limit is 100 mol%. If it is less than 50 mol%, CTE and CHE increase, and use as an insulating material for electrical and electronic equipment such as flexible printed wiring boards tends to be difficult.

In one preferred embodiment of the present invention, a polyimide resin (resin α) containing the following general formula (1) having an amide bond or an imide bond as a constituent unit is used as one component, and further an amide bond or an imide bond is formed. The polymer blend composition containing, as another component, a polyimide resin (resin β) having a composition different from that of the resin α, containing the following general formula (2) and / or general formula (3) as a structural unit. The resin β preferably includes the general formula (2). The composition ratio is preferably resin α / resin β = 99/1 to 1/99 weight ratio, more preferably 90/10 to 20/80 weight ratio, still more preferably 70/30 to 30/70 weight. Is the ratio. If the resin α / resin β exceeds 99/1 weight ratio, whitening and embrittlement due to the composition of the general formula (1) are likely to occur during molding into a film and the like, and the effect of improving its mechanical properties and adhesiveness Tend to be less. On the other hand, if the resin α / resin β is less than 1/99 weight ratio, the characteristics inherent to the resin α, particularly the characteristics such as low CTE property and low CHE property may not be maintained.
Resin β preferably contains 50 mol% or more of the structural unit of (general formula (2) + general formula (3)) when the total amine component and total acid component are 200 mol%, more preferably It is 70 mol% or more. The upper limit is 200 mol%. If it is less than 50 mol%, whitening and embrittlement are likely to occur, and the effect of improving the mechanical properties and adhesiveness is small. Moreover, in this invention, the structural unit of General formula (4) can be introduce | transduced and used for resin (beta).

(In general formula (1), R1 and R2 may be the same or different, and each represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group.)
(In the general formula (2), R3 and R4 may be the same or different, and each represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group. X is a direct bond, or
-SO2-, -O-, -CH2- is shown. )
(In general formula (3), X represents a direct bond or —SO 2 —, —O—, —CH 2 —).
(In the general formula (4), X represents a direct bond or —SO 2 —, —O—, —CH 2 —. In the general formula (2), general formula (3), and general formula (4), X represents They do not have to be the same and may be different.)

  Manufacture of the polyimide resin of this invention and a polyamide-imide resin is compoundable by a normal method. For example, there are an isocyanate method, an acid chloride method, a low temperature solution polymerization method, a room temperature solution polymerization method, etc., but from the viewpoint of production cost, a particularly preferable production method is an isocyanate method in which a polymer varnish can be obtained by a decarboxylation reaction. .

<Resin α>
Examples of the acid component and amine component used when polymerizing the resin α include the following.
As the acid component, 3, 3 ', 4, 4'-benzophenone tetracarboxylic acid, 3, 3', 4, 4, '-biphenyl tetracarboxylic acid, 3, 3', 4, 4'-diphenyl ether tetracarboxylic acid Or alkylene glycol bis (trimellitate), bisphenol bis (trimellitate), pyromellitic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, naphthalene-2 as shown by the following general formula (5) 3,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, monoanhydrides such as trimellitic acid, dianhydride The product or esterified product can be used alone or as a mixture of two or more.
(In the formula, R ′ represents an alkylene group or a divalent aromatic residue.)

By using the following monomer as the amine component, the structure of the general formula (1) can be introduced into the resin α. 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, 3,4'-diaminobiphenyl 3,3′-diaminobiphenyl, 4,4′-diaminobiphenyl and the like, or diisocyanates corresponding to these, or a mixture of two or more thereof can be used.

  In addition to the above, p-phenylenediamine, m-phenylenediamine, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, and 4,4′-diaminodiphenyl as long as the object of the present invention is not impaired. Sulfone, 3,3′-diaminodiphenylsulfone, 3,3′-diaminobenzanilide, 4,4′-diaminobenzanilide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3, 4'-diaminobenzophenone, 2,6-tolylenediamine, 2,4-tolylenediamine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Propane, 3,3′-diaminodiphenylpropane, 3,3′-diaminodiphenylmethane, 4 4'-diaminodiphenylmethane, P-xylenediamine, m-xylenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, 2,2'-bis (4-aminophenyl) 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] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3- Aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3 Aminophenoxy) biphenyl and the like, or may be used alone or two or more mixtures of amine components, such as a diisocyanate corresponding to these.

  Furthermore, dicarboxylic acid components such as isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, diphenyl ether-3,3 ′, 4′-tricarboxylic acid, diphenyl Monoanhydrides such as sulfone-3, 3 ′, 4′-tricarboxylic acid, dianhydrides, and esterified products can be used alone or as a mixture of two or more.

As the resin α, among the acid component and amine component, particularly preferred combinations are as follows.
Trimellitic anhydride as acid component, 3,3'-dimethyl-4,4'-diaminobiphenyl or 3,3'-dimethyl-4,4'-diisocyanatobiphenyl (O-tolidine diisocyanate) as amine component More preferably, the acid component is trimellitic anhydride, benzophenonetetracarboxylic dianhydride, or biphenyltetracarboxylic dianhydride as the acid component, and 3,3′-dimethyl-4,4 as the amine component. Polyamideimide resin composed of '-diisocyanatobiphenyl (O-tolidine diisocyanate) or 3,3'-dimethyl-4,4'-diaminobiphenyl.
<Acid component>
Trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.
<Amine component>
3,3′-dimethyl-4,4′-diaminobiphenyl or the corresponding diisocyanate.
In particular, biphenyltetracarboxylic dianhydride / benzophenone tetracarboxylic dianhydride) = 1/99 to 99/1 molar ratio, preferably biphenyltetracarboxylic dianhydride / benzophenone tetracarboxylic dianhydride = 30/70. ~ 70/30 molar ratio and {biphenyltetracarboxylic anhydride + benzophenonetetracarboxylic dianhydride} / trimellitic anhydride = 70 / 30-5 / 95 molar ratio, more preferably {biphenyltetracarboxylic acid A copolymerized polyamideimide resin satisfying the following relationship: anhydride + benzophenonetetracarboxylic dianhydride} / trimellitic anhydride = 50/50 to 10/90 molar ratio is desirable. In addition, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl (O-tolidine diisocyanate) or 3,3′-dimethyl-4,4′-diaminobiphenyl has a total amine component of 100 mol%. It is preferably a polyamide-imide resin copolymerized by 50 mol% or more, more preferably 70 mol% or more.
{Biphenyltetracarboxylic anhydride + benzophenonetetracarboxylic dianhydride} / trimellitic anhydride = When the ratio exceeds 70/30, the solubility in a solvent is basically poor, and a blend with resin β is formed. Tend to be difficult. Therefore, it is difficult to improve mechanical properties and adhesiveness.
Moreover, when the ratio is less than {biphenyltetracarboxylic anhydride + benzophenonetetracarboxylic dianhydride} / trimellitic anhydride = 5/95 molar ratio, characteristics such as CTE and CHE tend not to be expressed. Similarly, when 3,3′-dimethyl-4,4′-diisocyanatobiphenyl (O-tolidine diisocyanate) or 3,3′-dimethyl-4,4′-diaminobiphenyl is less than 50 mol%, CTE, CHE Therefore, it tends to be difficult to use as an insulating material for electrical and electronic equipment such as flexible printed wiring boards.

<Resin β>
In the resin β, the raw materials (acid component and amine component) used for introducing the general formula (2) and the general formula (3) into the polymer include the following.

If the following monomer is used as the acid component, the structure of the general formula (3) can be introduced into the resin β. Namely, biphenyl-3,3 ', 4,4'-tetracarboxylic acid, diphenylether-3,3', 4,4'-tetracarboxylic acid, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid , Monoanhydrides such as diphenylmethane tetracarboxylic acid, dianhydrides, and esterified products can be used.
When the structure of the general formula (4) is introduced into the resin β, diphenyl ether-3, 3 ′, 4′-tricarboxylic acid, diphenylsulfone-3, 3 ′, 4′-tricarboxylic acid, benzophenone-3 Monoanhydrides, dianhydrides, and esterified products such as 3 ′, 4′-tricarboxylic acid and the like can be used.

  If the following monomer is used as the amine component, the structure of the general formula (2) can be introduced into the resin β. That is, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 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, etc., or diisocyanates corresponding to these, or two or more Compounds can be used.

  Further, as the amine component of the resin β, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,4 ′ other than the amine component as long as the object of the present invention is not impaired. -Diaminobenzophenone, p-phenylenediamine, m-phenylenediamine, 3,3'-diaminobenzanilide, 4,4'-diaminobenzanilide, 2,6-tolylenediamine, 2,4-tolylenediamine, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 4,4′-diaminodiphenylpropane, 3,3′-diaminodiphenylpropane, P-xylenediamine, m-xylenediamine, 1,4- Naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine 2,2′-bis (4-aminophenyl) 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] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, or the corresponding diisocyanate alone Alternatively, a mixture of two or more kinds can be used.

Similarly, trimellitic acid, pyromellitic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, the following, in addition to the above acid component, as an acid component of resin β, within the range not impairing the object of the present invention: Alkylene glycol bis (trimellitate), bisphenol bis (trimellitate), naphthalene-2,3,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid, naphthalene as represented by the general formula (5) -1,4,5,8-tetracarboxylic acid monoanhydride, dianhydride, esterified product, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid Monoanhydrides, dianhydrides, esterified products such as acids, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, Dicarboxylic acids such as diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, and benzophenone dicarboxylic acid can be used alone or as a mixture of two or more.
(In the formula, R ′ represents an alkylene group or a divalent aromatic residue.)

Among the acid component and amine component, a particularly preferable combination is polyimide, copolyimide, polyamideimide, or copolyamideimide having as a main component a repeating unit selected from the following monomer components.
<Acid component>
Trimellitic anhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride.
<Amine component>
Diaminodiphenyl sulfone, diaminodiphenyl ether, diaminobenzophenone, diaminodiphenylmethane, 3,3′-dimethyl-4, 4′-diaminobiphenyl, or their corresponding diisocyanates.
As a preferred combination of the above acid component and amine component, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride is excellent particularly from the viewpoint of compatibility with the resin α as the acid component. 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and 3,3′-dimethyl-4,4′-diisocyanate biphenyl or 3,3′-dimethyl-4,4′-diamino as an amine component A combination of biphenyls is preferred. Also, it contains trimellitic anhydride as the acid component, and as the amine component, diaminodiphenylsulfone or diphenylsulfone diisocyanate, diaminodiphenylmethane or diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diaminobiphenyl or 3,3 ′ Polyamideimide resin containing at least one member selected from the group of -dimethyl-4,4'-diisocyanate biphenyl and diaminodiphenyl ether or diphenyl ether diisocyanate is also preferable.
Here, when the structures of the general formula (1) and the general formula (2) are the same, there may be a case where the resin α and the resin β have the same composition. However, in the present invention, the resin α and the resin β The composition ratios are preferably different. That is, even when the structures of the general formula (1) and the general formula (2) are the same, the resin α can be obtained by changing other copolymerization components or changing the composition ratio. And the resin β are preferably not the same resin. For example, when 3,3′-dimethyl-4,4′-diaminobiphenyl is used as the amine component of the general formula (2) as the resin β, the polyimide skeleton and the polyamideimide skeleton represented by the general formula (1), that is, the resin α In the present invention, the resin α and the resin β are preferably different resins. Basically, in the present invention, the resin α and the resin β are preferably different in composition.

  The molecular weight of the polyimide resin and polyamideimide resin used in the present invention is 0.1 to 2.5 dl / g in N-methyl-2-pyrrolidone (polymer concentration 0.5 g / dl) and logarithmic viscosity at 30 ° C. And a molecular weight corresponding to 0.4 to 2.0 dl / g. If the logarithmic viscosity is less than 0.1 dl / g, the mechanical properties may be insufficient when formed into a molded product such as a film, and if it exceeds 2.5 dl / g, the solution viscosity becomes high. Is not preferable because it becomes difficult.

  The polyimide resin and polyamideimide resin of the present invention may use an end-capping monomer for blocking the end. For example, monocarboxylic acids such as phthalic anhydride and benzoic acid, monoanhydrides, monoamines such as aniline and phenyl isocyanate, monoisocyanates, and the like can be used.

  The molar balance of the acid component and amine component during production is preferably such that the acid / amine molar ratio is in the range of 1.10 to 0.90 molar ratio, and more preferably, the acid component becomes slightly excessive, 1.00 It is the range of -1.05 molar ratio. The purity of the anhydride in the acid component is preferably 95%, preferably 99% or more.

In the polymer blend composition of the present invention, the acid component and the amine component as described above are selected, and the polyimide skeleton represented by the general formula (1), the general formula (2) and / or the general formula (3) and / or By adopting a composition in which a polyamideimide skeleton is introduced, it is possible to suppress whitening and embrittlement when the film is formed, for example, while maintaining the low CTE, low CHE and the like inherent in the resin α. This is considered because the random crystalline structure peculiar to resin (alpha) is suppressed.
It is considered that the performance is improved by using the resin β including the structure of the general formula (2) and / or the general formula (3) as one component and preventing macro phase separation from the resin α.
In addition, it is surprising in the present invention that even if the CTE of the resin β itself is high, the low CTE property of the resin α can be maintained as a whole polymer blend.

<Polyimide resin solution, polyamideimide resin solution>
Examples of the solvent for producing the polyimide resin solution, the polyamideimide resin solution, and the polymer blend composition solution used in the present invention include N-methyl-2-pyrrolidone, N, N′-dimethylformamide, N, N '-Dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, sulfolane, dimethylsulfoxide, γ-butyrolactone, cyclohexanone, cyclopentanone, etc., preferably N-methyl-2-pyrrolidone, N, N′-dimethylacetamide.
Some of these can be replaced with hydrocarbon organic solvents such as toluene and xylene, ether organic solvents such as diglyme, triglyme and tetrahydrofuran, and ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone. The polymer blend composition solution (varnish) can be obtained by uniformly mixing the above two or more types of polyimide varnish and / or polyamideimide varnish dissolved in an organic solvent.

  If necessary, the resin solution of the present invention may be used for the purpose of improving various properties of a film, a metal laminate, or a flexible printed circuit board, for example, mechanical properties, electrical properties, slipperiness, flame retardancy, and the like. Other resins, organic compounds, and inorganic compounds may be mixed or reacted. For example, lubricant (silica, talc, silicone, etc.), adhesion promoter, flame retardant (phosphorus, triazine, aluminum hydroxide, etc.), stabilizer (antioxidant, UV absorber, polymerization inhibitor, etc.), plating activity Agents, organic and inorganic fillers (talc, titanium oxide, fluoropolymer fine particles, pigments, dyes, calcium carbide, etc.), silicone compounds, fluorine compounds, isocyanate compounds, blocked isocyanate compounds, acrylic resins, urethane resins, Resins such as polyester resin, polyamide resin, epoxy resin, phenol resin and organic compounds, or these curing agents, inorganic compounds such as silicon oxide, titanium oxide, calcium carbonate, iron oxide, etc. are within the range not hindering the object of the present invention. Can be used together.

  The polyimide resin solution (varnish), polyamideimide resin solution (varnish), or polymer blend composition solution (varnish) thus obtained can be selected from a wide range of concentrations of polyimide resin and polyamideimide resin. It is preferable to be about ˜40% by weight, particularly about 8 to 20% by weight. If the concentration is out of the above range, workability may be reduced.

<Film>
A film can be produced using the above polymer blend composition solution (varnish). For the polymer blend composition film, the polymer blend composition solution (varnish) is applied onto a support such as an endless belt, a drum or a carrier film, the coating film is dried, and in some cases, after the film is peeled off from the support It is formed by heat treatment.

(Dry)
In the present invention, the drying conditions after coating are not particularly limited, but generally after initial drying at a temperature 70 to 130 ° C. lower than the boiling point (Tb (° C.)) of the solvent used in the polymer blend composition solution. Further, it is preferable to further dry (heat treatment) at a temperature close to or above the boiling point of the solvent.
When the initial drying temperature is higher than (Tb-70) ° C., foaming occurs on the coated surface, and when the drying temperature is lower than (Tb-130) ° C., the drying time becomes longer and the productivity is lowered. 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 for the solvent remaining rate in the coating film to be about 5 to 40% under the above temperature conditions, but generally about 1 to 30 minutes, especially 2 ~ 15 minutes.

  The heat treatment conditions are not particularly limited, and may be dried at a temperature near or above the boiling point of the solvent, but is generally 150 ° C. to 500 ° C., preferably 250 ° C. to 400 ° C. If it is less than 150 degreeC, drying time will become long and productivity will fall. If it exceeds 500 ° C., the deterioration reaction may proceed depending on the resin composition, and the resin film may be brittle. The time required for the heat treatment may be an effective time that generally eliminates the solvent remaining rate in the coating film under the above temperature conditions, but is generally several minutes to several tens of minutes. Usually, heat treatment is performed by drying a certain amount of solvent in the above initial drying to form a self-supporting film, and then peeling off from the support, and further fixing the end of the self-supporting film to a pin or the like. Is preferable.

In the present invention, the initial drying and heat treatment may be performed under an inert gas atmosphere or under reduced pressure. Examples of the inert gas include nitrogen, carbon dioxide, helium, and argon, but it is preferable to use easily available nitrogen. Moreover, when performing under reduced pressure, it is preferable to carry out under the pressure of about 10 < ^-5 > -10 < ³ > Pa, preferably about 10 < ^-1 > -200 Pa.

  The polymer blend composition film of the present invention thus obtained is a tough film having a mechanical property, that is, high strength, high elongation and low elastic modulus, without impairing the low CTE property, low CHE property, etc. of the resin α. Can be obtained. Moreover, adhesiveness with various adhesives, such as an adhesive for attaching a reinforcing plate, can be improved.

In addition, although the thickness of the resin film can be selected from a wide range, it is generally about 5 to 100 μm, preferably about 10 to 50 μm, after being completely dried. When the thickness is less than 5 μm, the mechanical properties such as film strength and handling properties are inferior. On the other hand, when the thickness exceeds 100 μm, the properties such as flexibility and workability (drying property, coating property) are deteriorated. To do.
Moreover, you may perform a surface treatment as needed. For example, surface treatment such as hydrolysis, corona discharge, low temperature plasma, physical roughening, and easy adhesion coating treatment can be performed.

[Polymer blend film with resin layer laminated]
By providing a resin layer on at least one surface of the polymer blend film, it can be used as various functional films.
When the resin to be laminated is an adhesive, it can be used as an adhesive film. Although the use of this polymer blend film with an adhesive layer is not particularly limited, it exhibits excellent characteristics when used as a cover film or a base film of a flexible printed circuit board. The adhesive composition is not particularly limited, and acrylonitrile butadiene rubber (NBR) adhesive, polyamide adhesive, polyester adhesive, polyester urethane adhesive, epoxy resin, acrylic resin, polyimide resin, Adhesives such as polyamide imide resin and polyester imide resin can be used, but from the viewpoint of heat resistance, adhesion, bending resistance, etc., polyimide resin, polyamide imide resin, or a resin in which an epoxy resin is blended with these resins A composition is preferable, and the thickness of the adhesive layer is about 1 to 100 μm, preferably 5 to 50 μm.
Further, when the resin to be laminated is a heat resistant resin such as a polyimide resin, it can be used as a high heat resistant substrate material that can withstand high temperature mounting. For example, the laminated structure disclosed in Examples 6 to 10 can be used as a TAB substrate film (FC film) or a chip-on-flexible substrate material (COF substrate).
The thickness ratio of the adhesive, heat-resistant coating material layer and polymer blend composition layer is adhesive layer or heat-resistant coating layer / polymer blend composition layer / = 0.05 to 20, preferably 0.1 to 5. If it is lower than 0.05, it may be inferior in heat resistance such as adhesiveness or chip mounting property, and if it is higher than 20, it may be used in the electrical and electronic fields such as mechanical properties, reinforcing plate, etc. It tends to be inferior to the adhesiveness.
The lamination method is not particularly limited, and a conventionally well-known method can be applied. For example, the viscosity of the adhesive or heat-resistant resin solution that is the coating liquid can be adjusted with a roll coater, knife coater, doctor, blade coater, gravure coater, die coater, reverse coater, etc., and then applied to the polymer blend film. it can. Also, simultaneous application of an adhesive, a heat resistant resin solution and a polymer blend composition solution can be performed. There are no particular limitations on the drying conditions and heat treatment conditions of the laminated adhesive and heat-resistant resin layer, and the film forming method, and conventionally known methods can be applied. For example, it is preferable that after the initial drying at a temperature 70 to 130 ° C. lower than the boiling point (Tb (° C.) of the solvent to be used, further drying (heat treatment) at a temperature near or higher than the boiling point of the solvent. Application of the same conditions as the blend composition solution is possible.

<Metal laminate>
The metal laminate of the present invention is formed by applying a solution of the polymer blend composition directly on a metal foil or via an anchor layer, drying the coating film, and optionally heat-treating it. As the metal foil, copper foil, aluminum foil, steel foil, nickel foil, etc. can be used, composite metal foil that combines these, zinc, chromium, nickel, cobalt, molybdenum compounds, or alloys thereof, Metal foils treated with other metals can also be used. Electrolytic copper foil, rolled copper foil, etc. can be used. HA type rolled copper foil (for example, BHY-HA manufactured by Nikko Metal Co., Ltd.) or non-roughened type (for example, Mitsui Metal Co., Ltd.) NA-DFF manufactured by Nippon Electrolytic Co., Ltd., U-WZ manufactured by Furukawa Circuit Foil Co., Ltd., F0-WS, etc.) can also be suitably used. Although there is no limitation in particular about the thickness of metal foil, For example, metal foil of 3-50 micrometers can be used suitably. The metal foil is usually in the form of a ribbon, and its length is not particularly limited. Also, the width of the ribbon-like metal foil is not particularly limited, but is generally about 5 to 300 cm, and preferably about 10 to 150 cm.
The anchor layer is not particularly limited, and examples thereof include an adhesive and a heat resistant coating material (heat resistant resin such as polyimide resin). In the case of an adhesive, the adhesive function is improved, and in the case of a heat-resistant coating material, the thermal characteristics such as solder heat resistance and high-temperature mountability are improved. For example, the laminated structure disclosed in Examples 6 to 10 is used. Thus, it can also be used as a substrate film for TAB (FC film) or a chip-on-flexible substrate material (COF substrate).
The thickness ratio of the adhesive, heat-resistant coating material layer and polymer blend composition layer is adhesive layer or heat-resistant coating layer / polymer blend composition layer / = 0.05 to 20, preferably 0.1 to 5. If it is lower than 0.05, it may be inferior in heat resistance such as adhesiveness or chip mounting property, and if it is higher than 20, it may be used in the electrical and electronic fields such as mechanical properties, reinforcing plate, etc. It tends to be inferior to the adhesiveness.

(Coating)
In the present invention, the polymer blend composition solution is applied directly to the metal foil or via an anchor layer and dried. The application method is not particularly limited, and a conventionally well-known method can be applied. For example, after adjusting the viscosity of the polymer blend composition solution, which is a coating solution, using a roll coater, knife coater, doctor, blade coater, gravure coater, die coater, reverse coater, etc., directly on the metal foil or anchor layer It can be applied via.

  The anchor layer composition when applied via the anchor layer is not particularly limited, and one preferred example is an acrylonitrile butadiene rubber (NBR) adhesive, a polyamide adhesive, a polyester adhesive, a polyester urethane system. Adhesives such as adhesive, epoxy resin, acrylic resin, polyimide resin, polyamideimide resin, and polyesterimide resin can be used. In this case, the adhesiveness with the metal foil is improved. From the viewpoint of heat resistance, adhesiveness, bending resistance, etc., preferably a polyimide resin system, a polyamideimide resin system, or a resin composition in which an epoxy resin is blended with these resins, the thickness of the adhesive layer is about 1 to 100 μm. The thickness is preferably 5 to 50 μm. The thickness of the adhesive is not particularly limited, but if the thickness is too thin, it may be difficult to obtain sufficient adhesion, while if the thickness is too thick, the workability (drying property, (Coating property) may be deteriorated.

As a means for forming a laminated structure through an adhesive layer, for example, the polymer blend composition film and the metal foil can be bonded together by a method such as heat lamination with the above-mentioned adhesive. In this case, the adhesive can be laminated on either the metal foil or the polymer blend composition film, or the polymer blend composition film on which the adhesive is laminated can be used as a film with an adhesive. it can. Alternatively, the metal foil and the polymer blend composition film can be bonded together by using an adhesive formed into a sheet as the adhesive sheet. There are no particular limitations on the drying conditions, heat treatment conditions, and the like of the laminated adhesive layers, and conventionally known methods can be applied. For example, it is preferable that after the initial drying at a temperature 70 to 130 ° C. lower than the boiling point (Tb (° C.) of the solvent to be used, further drying (heat treatment) at a temperature near or higher than the boiling point of the solvent. Application of the same conditions as drying and heat treatment of the blend composition solution is possible, and conventionally known methods can be applied as the bonding conditions.
In addition, as a means for forming a laminated structure through the adhesive layer, the above adhesive solution is directly applied to the metal foil and dried, and then the polymer blend composition solution is applied and dried. It can also be laminated. Specifically, an adhesive layer is applied to a metal foil, and after initial drying to a tack-free state, the polymer blend composition solution is then applied and initially dried. It can be produced by solvent removal drying (heat treatment) to such an extent that the solvent residual rate is eliminated. It can also be produced by coating the adhesive layer, initial drying and solvent removal (heat treatment), then applying the polymer blend composition solution, then initial drying and solvent removal (heat treatment). Alternatively, after the adhesive is applied, the polymer blend composition solution is applied, and initial drying and solvent removal can be performed. The method for applying the adhesive is not particularly limited, and a conventionally well-known method can be applied. For example, the viscosity of the solution of the adhesive composition that is a coating liquid can be adjusted by a roll coater, knife coater, doctor, blade coater, gravure coater, die coater, reverse coater, etc., and then applied to the metal foil. Moreover, simultaneous application | coating of an adhesive agent and a polymer blend composition solution can also be performed. There are no particular limitations on the drying conditions and heat treatment conditions of the laminate, and conventionally known methods can be applied. For example, it is preferable that after initial drying at a temperature 70 to 130 ° C. lower than the boiling point (Tb (° C.)) of the solvent to be used, further drying (heat treatment) at a temperature near or higher than the boiling point of the solvent. Application of the same conditions as drying and heat treatment of the blend composition solution is possible.

  As another preferred example of the anchor layer, a heat resistant coating material such as a heat resistant resin such as polyimide resin or polyamideimide resin can be used. The thickness of the heat-resistant coating layer is preferably about 1 to 100 μm, more preferably 5 to 50 μm. In this case, heat resistance such as solder heat resistance and mountability is improved, and it can be used as a high heat resistant substrate material.

A preferred composition for the anchor layer is, for example, a polyamideimide resin having a naphthalene skeleton disclosed in JP-A-2005-325329. As an acid component, trimellitic anhydride and / or 3,3 ′, 4,4′-benzophenonetetracarboxylic acid and / or 3,3 ′, 4,4, ′-biphenyltetracarboxylic acid, and / or Alternatively, pyromellitic anhydride and / or dicarboxylic acid such as terephthalic acid or isophthalic acid can be used. As the amine component, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, or diisocyanate corresponding to these can be used.
From the heat resistance and workability (solution moldability), trimellitic anhydride, 3,3 ′, 4,4′-benzophenone-tetracarboxylic acid, 3,3 ′, 4,4, ′-biphenyl-tetracarboxylic acid, The preferred ratio of pyromellitic anhydride, terephthalic acid, and isophthalic acid is trimellitic anhydride / 3,3 ′, 4,4′-benzophenone-tetracarboxylic acid / 3,3 ′, 4,4, ′-biphenyl- Tetracarboxylic acid / pyromellitic anhydride / terephteric acid and / or isophthalic acid = 5-50 / 10-60 / 5-5 / 40 / 1-20 / 0-30 (molar ratio) are preferred, more preferably Trimellitic anhydride / 3,3 ′, 4,4′-benzophenone tetracarboxylic acid / 3,3 ′, 4,4′-biphenyltetracarboxylic acid / pyromellitic anhydride / terephthelic acid and / or isophthal = 20 to 40 / 30-50 / 10-30 / 5-15 / 0-20 (molar ratio).
When the total acid component is 100 mol% and the total amine component is 100 mol%, the component having a naphthalene skeleton is preferably contained in an amount of 50 mol% to 200 mol%, more preferably 80 mol% to 180 mol%. It is.
In particular, it contains trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4, ′-biphenyltetracarboxylic acid, pyromellitic anhydride as an acid component, and A polyamideimide resin containing 1,5-naphthalenediamine or 1,5-naphthalene diisocyanate as the amine component is preferred.
For example, the laminated structure disclosed in Examples 6 to 10 can be used as a TAB substrate film (FC film) or a chip-on-flexible substrate material (COF substrate).

  A blend composition obtained by blending a polyamide-based resin having a naphthalene skeleton with a polyimide resin (polyimide resin and / or polyamide-imide resin) containing a biphenyl skeleton is also heat resistant, adhesive, dimensional stability, flexibility, insulation. Can be suitably used as an anchor layer from the balance of properties such as properties (migration resistance) and moisture absorption properties. When the total amount of the biphenyl skeleton is 100 mol% and the total amount of the amine component is 100 mol%, it is preferable that the biphenyl skeleton is copolymerized more than 50 mol% in total of the acid component and the amine component, more preferably. Is copolymerized in an amount of 70 mol% or more. As a resin containing a biphenyl skeleton, a polyamideimide resin containing 3,3′-dimethyl-4,4′-diaminobiphenyl or 3,3′-dimethyl-4,4′-diisocyanate biphenyl as an essential component is used as an amine component. More preferably, 3,3′-dimethyl-4,4′-diaminobiphenyl is included as an amine component, and trimellitic anhydride, benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride are essential components of the acid component. Polyamideimide resin contained as a component.

  The preferable amount of the polyimide resin containing the biphenyl skeleton to be blended is preferably 5% by weight to 70% by weight in terms of solid content (weight ratio) when the total amount of the resin used for the anchor layer is 100% by weight. Preferably they are 10 weight%-50 weight%, More preferably, they are 20 weight%-40 weight%. If it is less than 5% by weight or more than 70% by weight, it is effective for balancing various performances as a flexible printed circuit board, such as heat resistance, adhesiveness, dimensional stability, flexibility, insulation (migration resistance), and moisture absorption characteristics. Tend to be less.

  In addition, the polyamideimide resin having the naphthalene skeleton and the polyimide resin containing the biphenyl skeleton to be blended and / or the polyamideimide resin may be a polyamic acid resin which is a precursor of polyimide or polyamideimide. It is effective in balancing various performances as a flexible printed circuit board, such as dimensional stability, flexibility, insulation (migration resistance), and moisture absorption characteristics.

The acid component and amine component which can be used for the polyimide resin and / or polyamideimide resin containing the biphenyl skeleton to blend are illustrated below.
<Acid component>
Trimellitic anhydride, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, diphenylethertetracarboxylic acid, naphthalenetetracarboxylic acid monoanhydride, dianhydride, esterified product alone or a mixture of two or more.
<Amine component>
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 or the corresponding diisocyanate alone or 2 A mixture of more than seeds.

In particular, biphenyltetracarboxylic anhydride / benzophenonetetracarboxylic dianhydride) = 1/99 to 99/1 molar ratio, more preferably biphenyltetracarboxylic anhydride / benzophenonetetracarboxylic dianhydride = 30/70 to 70/30 molar ratio and {biphenyltetracarboxylic anhydride + benzophenonetetracarboxylic dianhydride} / trimellitic anhydride = 70 / 30-5 / 95 molar ratio, preferably {biphenyltetracarboxylic anhydride Copolymer polyamideimide satisfying the following formula: product + benzophenonetetracarboxylic dianhydride} / trimellitic anhydride = 50/50 to 10/90 molar ratio. Further, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl (O-tolidine diisocyanate) is copolymerized in an amount of 50 mol% or more, preferably 70 mol% or more when the total amine component is 100 mol%. It is preferable to do.
{Biphenyltetracarboxylic anhydride + benzophenonetetracarboxylic dianhydride} / trimellitic anhydride = When 70/30 molar ratio is exceeded, the solubility in a solvent is basically poor, and {biphenyltetracarboxylic anhydride Product + benzophenone tetracarboxylic dianhydride} / trimellitic anhydride = less than 5/95 molar ratio, flexible in heat resistance, adhesiveness, dimensional stability, flexibility, insulation (migration resistance), moisture absorption characteristics, etc. It becomes difficult to balance various performances as a printed circuit board. The same applies even when 3,3′-dimethyl-4,4′-diisocyanatobiphenyl (O-tolidine diisocyanate) is less than 50 mol%.

As a means for forming a laminated structure through a heat-resistant coating layer, for example, the polymer blend composition film and the metal foil can be bonded together by a method such as heating lamination through the heat-resistant coating material. In this case, the heat-resistant coating material can be laminated on either a metal foil or a polymer blend composition film, and the polymer blend composition film on which the heat-resistant coating material is laminated is used as a film with a heat-resistant coating material. You can also Alternatively, a sheet as a heat-resistant sheet can be formed, and a metal foil and a polymer blend composition film can be bonded as an adhesive sheet. There are no particular limitations on the drying conditions and heat treatment conditions of the laminated heat-resistant coating material layer, and conventionally known methods can be applied. For example, it is preferable that after initial drying at a temperature 70 to 130 ° C. lower than the boiling point (Tb (° C.)) of the solvent to be used, further drying (heat treatment) at a temperature near or higher than the boiling point of the solvent. Application of the same conditions as drying and heat treatment of the blend composition solution is possible, and conventionally known methods can be applied as the bonding conditions.
In addition, as a means for forming a laminated structure through the heat-resistant coating material layer, the above-mentioned heat-resistant coating material solution is directly applied to the metal foil and dried, and then the polymer blend composition solution is applied and dried. It can also be laminated. Specifically, a heat-resistant coating material layer is applied to a metal foil, and after initial drying to a tack-free state, the polymer blend composition solution is then applied and initially dried, and finally in the coating film The solvent can be produced by removing the solvent to the extent that the residual solvent ratio is eliminated (heat treatment). It is also possible to manufacture by coating a heat-resistant coating material layer, initial drying and solvent removal (heat treatment), then applying the polymer blend composition solution, then initial drying and solvent removal (heat treatment). Alternatively, after the heat-resistant coating material is applied, the polymer blend composition solution is applied, initial drying, and desolvation can be performed. The method for applying the heat-resistant coating material is not particularly limited, and a conventionally well-known method can be applied. For example, the viscosity of the heat-resistant coating material solution that is a coating solution can be adjusted by a roll coater, a knife coater, a doctor, a blade coater, a gravure coater, a die coater, a reverse coater, etc., and then applied to the metal foil. In addition, the heat-resistant coating material and the polymer blend composition solution can be applied simultaneously. There are no particular limitations on the drying conditions and heat treatment conditions of the laminate, and conventionally known methods can be applied. For example, it is preferable that after initial drying at a temperature 70 to 130 ° C. lower than the boiling point (Tb (° C.)) of the solvent to be used, further drying (heat treatment) at a temperature near or higher than the boiling point of the solvent. The same conditions as the drying and heat treatment conditions of the blend composition solution can be applied.

(Dry)
In the present invention, the drying conditions after coating are not particularly limited, but generally after initial drying at a temperature 70 to 130 ° C. lower than the boiling point (Tb (° C.)) of the solvent used in the polymer blend composition solution. Further, it is preferable to further dry (heat treatment) at a temperature close to or above the boiling point of the solvent.
When the initial drying temperature is higher than (Tb-70) ° C., foaming occurs on the coated surface, or unevenness of the residual solvent in the thickness direction of the resin layer increases, so that the metal laminate is warped (curl). There is also a large warp of a flexible printed circuit board obtained by processing the circuit.

  Moreover, when drying temperature is lower than (Tb-130) degreeC, drying time will become long and productivity will fall. 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 for the solvent remaining rate in the coating film to be about 5 to 40% under the above temperature conditions, but generally about 1 to 30 minutes, especially 2 ~ 15 minutes.

  The heat treatment conditions are not particularly limited, and may be dried at a temperature near or above the boiling point of the solvent, but is generally 150 ° C. to 500 ° C., preferably 250 ° C. to 400 ° C. If it is less than 150 degreeC, drying time will become long and productivity will fall. If it exceeds 500 ° C., the deterioration reaction proceeds depending on the resin composition, and the resin film becomes brittle. The time required for the heat treatment may be an effective time that generally eliminates the solvent remaining rate in the coating film under the above temperature conditions, but is generally several minutes to several tens of minutes.

In the present invention, drying and heat treatment may be performed under an inert gas atmosphere or under reduced pressure. Examples of the inert gas include nitrogen, carbon dioxide, helium, and argon, but it is preferable to use easily available nitrogen. Moreover, when performing under reduced pressure, it is preferable to carry out under the pressure of about 10 < ^-5 > -10 < ³ > Pa, preferably about 10 < ^-1 > -200 Pa.

  In the present invention, both the initial drying and the heat treatment are not particularly limited, but can be performed by a conventionally known method such as a roll support method or a floating method. Moreover, continuous heat treatment in a heating furnace such as a tenter type is also possible.

The metal laminate of the present invention thus obtained does not impair the low CTE property, low CHE property, etc. of the resin α, and the mechanical properties of the insulating resin layer, that is, high strength, high elongation and low elastic modulus. A metal laminate obtained by laminating a tough film can be obtained, and adhesion with various adhesives such as an adhesive for attaching a reinforcing plate can be improved.
In addition, although the thickness of the resin film layer can be selected from a wide range, it is generally about 5 to 100 μm, preferably about 10 to 50 μm, after being completely dried. When the thickness is less than 5 μm, the mechanical properties such as film strength and handling properties are inferior. On the other hand, when the thickness exceeds 100 μm, the properties such as flexibility and workability (drying property, coating property) are deteriorated. To do.
Moreover, you may perform a surface treatment as needed. For example, surface treatment such as hydrolysis, corona discharge, low temperature plasma, physical roughening, and easy adhesion coating treatment can be performed.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not particularly limited by the examples. The evaluation method of the characteristic value in each example is as follows. In addition, the powdery polymer sample used for evaluation was prepared by reprecipitation and purification of the polymerization solution obtained in each Example with a large amount of acetone.

[X-ray measurement]
Measurement method: Wide-angle X-ray diffraction transmission method Output: 40 kV-200 mA
Scanning speed: 1 ° / min Sample size: 15 mm x 3 mm, 3 layers [logarithmic viscosity]
Using a powdered polymer sample, it was dissolved in N-methyl-2-pyrrolidone so that the polymer concentration would be 0.5 g / dl, and the solution viscosity and solvent viscosity of the solution were 30 ° C. with an Ubbelohde type viscosity tube. Measured and calculated by the following formula.
Logarithmic viscosity (dl / g) = [ln (V1 / V2)] / V3
In the above formula, V1 represents the solution viscosity measured with an Ubbelohde type viscosity tube, V2 represents the solvent viscosity measured with an Ubbelohde type viscosity tube, and V1 and V2 represent a polymer solution and a solvent (N-methyl-2-pyrrolidone). Was determined from the time taken to pass through the capillary of the viscosity tube. V3 is the polymer concentration (g / dl).

[Glass-transition temperature]
The glass transition temperature of the resin film of the present invention was measured under the following conditions by TMA (Thermomechanical Analysis / manufactured by Rigaku Corporation) tensile load method. The film was measured for a film that was once heated to an inflection point in nitrogen at a heating rate of 10 ° C./min and then cooled to room temperature.
Load: 1g
Sample size: 4 (width) x 20 (length) mm
Temperature increase rate: 10 ° C / min Atmosphere: Nitrogen

[Coefficient of thermal expansion (CTE)]
The thermal expansion coefficient of the resin film of the present invention was measured under the following conditions by TMA (Thermomechanical Analysis / Rigaku Corporation) tensile load method. The film was measured for a film that was once heated to an inflection point in nitrogen at a heating rate of 10 ° C./min and then cooled to room temperature.
Load: 1g
Sample size: 4 (width) x 20 (length) mm
Temperature increase rate: 10 ° C / min Atmosphere: Nitrogen

[Film compatibility (transparency)]
The transparency of the prepared resin film having a thickness of 20 μm was visually observed.

<Adhesion>
In accordance with JISK5400, a cross-cut test was performed, and a residual rate of 100% was evaluated as ◯.

<Strength, elongation and elastic modulus of resin film>
A sample for measurement having a width of 10 mm and a length of 100 mm was prepared from a resin film, and a tensile tester (trade name “Tensilon Tensile Tester”, manufactured by Toyo Baldwin) had a tensile speed of 20 mm / min and a chuck distance (gross). ) Measured at 40 mm.
<Hygroscopic dimensional change rate; CHE>
It calculated | required with the following procedures.
(1) The resin varnish obtained in the synthesis example was subjected to solvent removal using a knife coater on an electrolytic copper foil having a thickness of 12 μm (trade name “NA-DFF”, manufactured by Mitsui Kinzoku Co., Ltd., Rz 0.6 μm). Coating was performed so that the thickness was 20 μm. Next, after drying for 5 minutes at a temperature of 100 ° C., heat treatment is performed at each temperature of 200 ° C., 250 ° C., and 300 ° C. for 30 minutes in a nitrogen atmosphere to form a metal laminate.
(2) According to IPC-FC 241 (IPC-TM-650, 2.2.4 (c)), a hole is made in a certain position of the metal laminate obtained in (1), and 25 ° C. and 65%. Measure humidity for 4 hours and measure the distance between holes.
(3) The entire surface of the metal layer of the metal laminate was removed (etched) with ferric chloride, and the resulting resin film was subjected to 25 ° C. in each atmosphere having a relative humidity of 20%, 40%, 65%, and 90%. For 4 hours.
(4) According to IPC-FC 241 (IPC-TM-650, 2.2.4 (c)), the distance between holes in the resin film is measured, and the distance between holes in the metal foil laminate in (2). The dimensional change rate is obtained based on the above.
(5) The dimensional change rate of (4) is plotted against each relative humidity, and the slope with respect to the humidity is defined as the hygroscopic dimensional change rate.

Synthesis Example 1 (Synthesis of Resin A)
Trimellitic anhydride 115.3 g (60 mol%), 3, 3 ′, 4, 4′-benzophenone tetracarboxylic dianhydride 32.2 g (10 mol%), 3, 3 ′, 4, 4 in a reaction vessel '-Biphenyltetracarboxylic dianhydride 88.3 g (30 mol%), 3,3'-dimethyl-4,4'-biphenyldiisocyanate (O-tolidine diisocyanate) 264.3 g (100 mol%), and N -2500 g of methyl-2-pyrrolidone and 1.5 g of diazabicyclo [5.4.0] undecene-7 were added, the temperature was raised to 100 ° C. under a nitrogen stream, and the mixture was reacted at 100 ° C. for 5 hours. Then, it was diluted with N-methyl-2-pyrrolidone until the polymer concentration became 12% by weight and cooled to room temperature. The logarithmic viscosity and the like of the obtained polymer are as shown in Table-1.

Synthesis Example 2 (Synthesis of Resin B)
In a reaction vessel, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 358 g, 3,3′-dimethyl-4,4′-diisocyanate biphenyl 264.3 g (100 mol%), and N— 3000 g of methyl-2-pyrrolidone and 1.5 g of triethylenediamine were added, the temperature was raised to 100 ° C. under a nitrogen stream, and the reaction was carried out at 100 ° C. for 3 hours. Next, the mixture was reacted at 160 ° C. for 2 hours, diluted with N-methyl-2-pyrrolidone until the polymer concentration became 12% by weight, and cooled to room temperature. The logarithmic viscosity and the like of the obtained polymer are as shown in Table-1.

Synthesis Example 3 (Synthesis of Resin C)
In a reaction vessel, 179 g (50 mol%) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 96 g (50 mol%) of trimellitic anhydride, 250 g of 4,4′-diphenylmethane diisocyanate (100 Mol%), 2500 g of N-methyl-2-pyrrolidone and 1.5 g of triethylenediamine were added, the temperature was raised to 100 ° C. in a nitrogen stream, and the mixture was reacted at 100 ° C. for 5 hours. Next, the mixture was reacted at 160 ° C. for 2 hours, diluted with N-methyl-2-pyrrolidone until the polymer concentration became 12% by weight, and cooled to room temperature. The logarithmic viscosity and the like of the obtained polymer are as shown in Table-1.

Synthesis Example 4 (Synthesis of Resin D)
Trimellitic anhydride 192 g (100 mol%), 4,4′-diphenylmethane diisocyanate 250 g (100 mol%), N-methyl-2-pyrrolidone 2500 g and potassium fluoride 0.5 g were added to the reaction vessel, and nitrogen was added. The temperature was raised to 100 ° C. under an air stream, and the reaction was carried out at 100 ° C. for 3 hours. Subsequently, it diluted with N-methyl-2-pyrrolidone until the polymer concentration became 12 weight%, and it cooled to room temperature. The logarithmic viscosity of the obtained polymer was as shown in Table-1.

Synthesis Example 5 (Synthesis of Resin E)
In a reaction vessel, 192 g (100 mol%) trimellitic anhydride, 252 g (100 mol%) of 4,4′-diphenyl ether diisocyanate, 2500 g of N-methyl-2-pyrrolidone, diazabicyclo [5.4.0] undecene- 7, 1.5g was added, it heated up to 100 degreeC under nitrogen stream, and it was made to react at 100 degreeC for 3 hours. Next, the mixture was reacted at 160 ° C. for 2 hours, diluted with N-methyl-2-pyrrolidone until the polymer concentration became 12% by weight, and cooled to room temperature. The logarithmic viscosity of the obtained polymer was as shown in Table-1.

Synthesis Example 6 (Synthesis of Resin F)
In a reaction vessel, 192.1 g (100 mol%) trimellitic anhydride, 211.4 g (80 mol%) of 3,3′-dimethyl-4,4′-diisocyanate biphenyl, 34.8 g of 2,4-tolylene diisocyanate ( 20 mol%), and 2500 g of N-methyl-2-pyrrolidone and diazabicyclo [5.4.0] undecene-7, 1.5 g were added, and the temperature was raised to 100 ° C. under a nitrogen stream, and at 100 ° C. for 5 hours. Reacted. Then, it was diluted with N-methyl-2-pyrrolidone until the polymer concentration became 12% by weight and cooled to room temperature. The logarithmic viscosity of the obtained polymer was as shown in Table-1.

Synthesis Example 7 (Synthesis of Resin G)
In a reaction vessel, trimellitic anhydride 58 g (30 mol%), 3, 3 ′, 4, 4′-benzophenone tetracarboxylic dianhydride 129 g (40 mol%), 3, 3 ′, 4, 4′-biphenyl tetra Carboxylic dianhydride 58 g (20 mol%), pyromellitic anhydride 22 g (10 mol%), 1,5-naphthalene diisocyanate 210 g (100 mol%), diazabicyclo [5.4.0] undecene-7, 1 g And 1836 g of N-methyl-2-pyrrolidone were added, the temperature was raised to 100 ° C. over 2 hours, and the reaction was allowed to proceed for 5 hours. Subsequently, it diluted with N-methyl-2-pyrrolidone so that a polymer concentration might be 12 weight%, and it cooled to room temperature. The logarithmic viscosity of the obtained polymer was as shown in Table-1.

Synthesis Example 8 (Synthesis of Resin H)
Add 248 g of 4,4'-diaminodiphenylsulfone, 2500 g of N-N'-dimethylacetamide (DMAC) and 130 g of triethylamine to the reaction vessel, add a DMAC solution of 210 g of trimellitic anhydride chloride while stirring vigorously, and stir for 30 minutes. did. The obtained reaction mixture was poured into a large amount of water, and the product was separated and filtered. After washing with water, the pressure was reduced at 60 ° C. to obtain a polyamideimide precursor. Next, the varnish was adjusted with N-methyl-2-pyrrolidone so that the polymer concentration was 12% by weight. The logarithmic viscosity (precursor) of the obtained polymer was as shown in Table 1.
<Creation of resin A to resin H film>
The resin varnishes of Synthesis Examples 1 to 8 were applied to a PET film having a thickness of 100 μm with a knife coater so that the thickness after drying was 20 μm. Subsequently, it dried until it became a transparent and tack-free state at a temperature of 50 ° C. to 100 ° C., and then peeled from the PET film to obtain a self-supporting film. The obtained film was fixed to the stainless steel frame at the ends of the upper and lower surfaces and the left and right surfaces, and heat-treated at a temperature of 230 to 300 ° C. for 30 to 60 minutes under vacuum. About the created film, Tg and CTE were measured. (Table 1)

<Production Examples of Polymer Blend Composition Film (Examples 1 to 5, Example 21, Comparative Example 1)>
After blending the resin varnish A obtained in Synthesis Example 1 and the resin varnishes B to F and H obtained in Synthesis Examples 2 to 6 and 8 so that the solid content weight ratio is 1/1, each Depending on the mixing state of the varnish, it was diluted with N-methyl-2-pyrrolidone to an appropriate concentration and then homogenized to obtain a transparent polymer blend composition varnish.
The prepared resin varnish was applied to a PET film having a thickness of 100 μm with a knife coater so that the thickness after drying was 20 μm. Subsequently, it dried until it became a transparent and tack-free state at a temperature of 50 ° C. to 100 ° C., and then peeled from the PET film to obtain a self-supporting film.
The obtained film was heat treated under conditions of 330 ° C. for 1 minute in a nitrogen atmosphere with the edges of the upper and lower surfaces and the left and right surfaces fixed to a stainless steel frame. The obtained film characteristics were as shown in Table 2.
For comparison, a film was prepared under the same conditions using the resin varnish A of Synthesis Example 1 only. The obtained film was not transparent, and a crystal structure was recognized as shown in FIG. The properties of the film are shown in Table 2.
<Examples of production of polymer blend composition film (Examples 22 to 25)>
In the same manner as described above, the resin varnish A obtained in Synthesis Example 1 and the resin varnishes B to E obtained in Synthesis Examples 2 to 5 were prepared so that the solid content weight ratio was 7/3. The obtained film characteristics were as shown in Table 3.
<Production Example of Polymer Blend Composition Film (Examples 26 to 29)>
In the same manner as described above, the resin varnish A obtained in Synthesis Example 1 and the resin varnishes B to E obtained in Synthesis Examples 2 to 5 were made to have a solid content weight ratio of 3/7 to produce a film. The obtained film characteristics were as shown in Table 4.

<Example 1 of production of metal laminate with anchor layer-1
(Examples 6 to 10, Examples 30 to 38, Comparative Example 2)>
The resin varnish G obtained in Synthesis Example 7 was subjected to solvent removal using a knife coater on an electrolytic copper foil (trade name “U-WZ”, manufactured by Furukawa Circuit Foil Co., Ltd., Rz 0.6 μm) having a thickness of 12 μm. Coating was performed so that the thickness was 10 μm (anchor layer). Next, after drying at a temperature of 100 ° C. for 3 minutes, heat treatment was performed at 350 ° C. for 1 minute to obtain a metal laminate.
The thickness of the polymer blend composition varnish used in Examples 1 to 5, Examples 21 to 29, and Comparative Example 1 and the resin A alone after solvent removal on the resin surface of the metal laminate is 30 μm. (Top layer). Next, after drying at a temperature of 100 ° C. for 3 minutes, heat treatment was performed at 330 ° C. for 3 minutes to obtain a metal laminate with an anchor layer.
About the obtained metal laminated body, the adhesiveness between an anchor layer and a top layer was evaluated by grid peeling. The results are as shown in Table 5. The resin varnish used in Comparative Example 1 was peeled off at the interface with the anchor layer, but the others showed good adhesion.
<Example-2 of production of metal laminate with anchor layer-2
(Examples 11 to 15, Examples 39 to 47, Comparative Example 3)>
A metal laminate with an anchor layer in the same manner as in Production Example 1 except that the anchor varnish G is replaced with a resin varnish G and a resin varnish A blend varnish (solid content weight ratio is 1/1). Got. About the obtained metal laminated body, the adhesiveness between an anchor layer and a top layer was evaluated by grid peeling. Adhesion due to cross-cut peeling was as shown in Table 6.

<Examples of metal laminate production (Examples 16 to 20, Examples 48 to 56, Comparative Example 4)>
The resin solutions used in Examples 1 to 5, Examples 21 to 29, and Comparative Example 1 were made into a rolled copper foil having a thickness of 18 μm; BHY-HA foil (trade name “BHYA-13F-HA”, Nippon Mining & Metals Co., Ltd. ), Rz 0.7 μm), using a knife coater, coating was performed so that the thickness after solvent removal was 20 μm. Next, after drying at a temperature of 100 ° C. for 3 minutes, heat treatment was performed at 350 ° C. for 1 minute to obtain a metal laminate.
The resin surface of the obtained metal laminate was coated with a resin varnish manufactured by Toyobo Co., Ltd. and Viromax HR11NN so as to have a thickness after solvent removal of 15 μm as an adhesive for reinforcing plates. Subsequently, after drying for 3 minutes at the temperature of 100 degreeC, it heated at 350 degreeC for 1 minute, and obtained the laminated body.
About the obtained laminated body, the adhesiveness of a polymer blend resin layer and an adhesive bond layer was evaluated by cross-cut peeling. Table 7 shows the results of evaluation of adhesion by cross-cut peeling.

  According to the present invention, it is possible to obtain a tough film metal laminate having mechanical properties, that is, high strength, high elongation and low elastic modulus. Moreover, a polymer blend composition, a film, and a metal laminate having excellent adhesion to various adhesives such as an adhesive for attaching a reinforcing plate can be obtained. In particular, a polymer blend composition, a film, and a metal having improved mechanical properties and adhesion while maintaining the properties of polyimide and polyamideimide having an O-tolidine skeleton excellent in low CTE properties, low CHE properties, etc. Since the laminate can be obtained with high productivity, it is industrially useful.

Claims (10)

A polymer blend composition comprising a mixture of two or more components of a polyimide resin and the following (a) to (c) :
(A) One component of the polyimide resin to be mixed is a polyimide resin (resin α) containing the following general formula (1) as a structural unit;
(In general formula (1), R1 and R2 may be the same or different, and each represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group.)
(B) One component of the polyimide resin to be mixed is a polyimide resin (resin β) having a composition different from that of the resin α, and includes the following general formula (2) and / or general formula (3) as a structural unit. about;
(In the general formula (2), R3 and R4 may be the same or different and each represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group. X represents a direct bond, —SO ₂ — , -O-, or -CH _2- .)
(In the general formula (3), X represents a direct bond, —SO ₂ —, —O—, or —CH ₂ —. In the general formula (2) and general formula (3), X may be different from each other. good.)
(C) The weight ratio of the resin α and the resin β is resin α / resin β = 90/10 to 20/80. The ratio of the general formula (1) in the resin α is 50 mol% or more when the total amine component is 100 mol%, and
When the total amine component and the total acid component in the resin β are 200 mol%, the structural unit of the general formula (2) and / or the general formula (3) is included in an amount of 50 mol% or more.
The polymer blend composition according to claim 1. Resin α contains trimellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride as an acid component, and 3,3′-dimethyl-4,4′-diaminobiphenyl or 3,3 as an amine component The polymer blend composition according to claim 1 or 2, which is a polyamide-imide resin containing 3'-dimethyl-4,4'-diisocyanatobiphenyl. The polymer blend composition according to any one of claims 1 to 3, wherein the resin β is a polyimide resin containing 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride as an acid component. . Resin β contains 3,3′-4,4′-diphenylsulfonetetracarboxylic dianhydride as an acid component, and 3,3′-dimethyl-4,4′-diaminobiphenyl or 3,3 ′ as an amine component The polymer blend composition according to any one of claims 1 to 4, which is a polyimide resin containing -dimethyl-4,4'-diisocyanate biphenyl. Resin β contains trimellitic anhydride as the acid component, and as the amine component, diaminodiphenylsulfone or diphenylsulfone diisocyanate, diaminodiphenylmethane or diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diaminobiphenyl or 3, 3. A polyamide-imide resin characterized by comprising at least one member selected from the group consisting of 3'-dimethyl-4,4'-diisocyanate biphenyl and diaminodiphenyl ether or diphenyl ether diisocyanate. A polymer blend composition according to any of the above. The film which consists of a polymer blend composition in any one of Claims 1-6. A film having at least one layer made of the film according to claim 7. A metal laminate in which the film according to claim 7 or 8 is laminated directly on at least one side of the metal foil or via an anchor layer. The anchor layer contains trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and pyro The metal laminate according to claim 9, comprising merit acid anhydride and 1,5-naphthalenediamine or 1,5-naphthalenediisocyanate as an amine component.