JP2016141752A - Polyarylate resin solution composition, production method of polyarylate resin film, polyarylate resin film, three-layer film, laminate, and printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylate resin solution composition or the like that exhibits excellent application property and electric characteristics when used for a laminate for a printed wiring board.SOLUTION: The polyarylate resin solution composition comprises: a polyarylate resin comprising a structural unit containing a divalent phenol and a structural unit derived from an aromatic dicarboxylic acid; and a solvent. The polyarylate resin contains a structural unit containing a divalent phenol and derived from a compound represented by general formula (1) by 20 mol% or more with respect to the total of structural units constituting the polyarylate resin; and the composition contains a cyclic ketone having 5 to 10 carbon atoms as the solvent.SELECTED DRAWING: None

Description

  The present invention relates to a polyarylate resin solution composition, a method for producing a polyarylate resin film, a polyarylate resin film, a three-layer film, a laminate, and a printed circuit board.

A laminated body in which a metal layer is provided on an insulating layer is used for a printed wiring board (printed circuit board or printed circuit board) incorporated in an electronic device such as a mobile phone, a personal computer, or a digital home appliance.
In recent years, polyarylate resins having excellent heat resistance and electrical characteristics have been adopted for these substrates (for example, Patent Documents 1 to 5).
On the other hand, since polyarylate resin is excellent in heat resistance and electrical characteristics, it is also expected as an adhesive layer of a laminate used for the above-mentioned printed wiring board. In order to improve the electrical characteristics of the printed wiring board, it is important to employ a resin composition used for the laminate.

JP 2013-173928 A JP 2009-167291 A JP-A-8-134336 JP 2011-68798 A JP 2003-313276 A

When adopting a polyarylate resin as an adhesive layer of a laminate used for a printed wiring board, in order to improve the applicability to the metal layer used for the laminate and the electrical characteristics of the printed wiring board using the laminate, There was still room for improvement in the polyarylate resin composition.
This invention is made | formed in view of the said situation, and when it uses for the laminated body for printed wiring boards, it aims at providing the polyarylate resin solution composition etc. which are excellent in applicability | paintability and an electrical property. .

  A first aspect of the present invention includes a polyarylate resin containing a structural unit containing a dihydric phenol and a structural unit derived from an aromatic dicarboxylic acid, and a solvent, and the polyarylate resin contains a dihydric phenol. Containing at least 20 mol% of structural units derived from a compound represented by the following general formula (1) with respect to the total of all the structural units constituting the polyarylate resin, It contains a C5-C10 cyclic ketone as a polyarylate resin solution composition.

［式（１）中、Ｒ^１〜Ｒ^４は、互いに独立に、水素原子、炭素数１〜１２の炭化水素基又はハロゲン原子を表す。
Ｒ^５およびＲ^６は、互いに独立に、水素原子又は炭素数１〜４の炭化水素基を表す。
ｍは、４〜７の整数を表す。
Ｘは、炭素原子を表す。
複数の−Ｘ（Ｒ^５）（Ｒ^６）−は、同一であってもよく異なってもよい。］

Wherein ^(1), R 1 ~R ^4, independently of each other, represent a hydrogen atom, a hydrocarbon group or a halogen atom having 1 to 12 carbon atoms.
R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
m represents an integer of 4 to 7.
X represents a carbon atom.
A plurality of —X (R ⁵ ) (R ⁶ ) — may be the same or different. ]

The second aspect of the present invention is characterized by comprising the steps of casting the polyarylate resin solution composition of the first aspect on a support substrate and removing the solvent from the solution composition. It is a manufacturing method of a polyarylate resin film.
A third aspect of the present invention is a polyarylate resin film obtained by the method for producing a polyarylate resin film of the second aspect.
In a fourth aspect of the present invention, layers are formed on both sides of the polyimide resin film using the polyarylate resin solution composition of the first aspect, and the thickness (T1) of the polyimide resin film and the first A three-layer film characterized in that the ratio (T1 / T2) of the thickness (T2) of the layers formed using the polyarylate resin solution composition of the embodiment is 2 to 20, wherein the two T2s are independent of each other They may be the same or different.)
A fifth aspect of the present invention is a laminated board characterized in that a metal layer is formed on at least one side of the three-layer film of the fourth aspect.
A sixth aspect of the present invention is a printed circuit board using the laminated board of the fifth aspect.

  ADVANTAGE OF THE INVENTION According to this invention, when used for the laminated body for printed wiring boards, the polyarylate resin solution composition etc. which are excellent in applicability | paintability and an electrical property can be provided.

It is a schematic diagram for demonstrating the three-layer film of this invention. It is a schematic diagram for demonstrating the laminated body using the three-layer film of this invention. It is the schematic for demonstrating the manufacturing method of the three-layer film of the 3rd aspect of this invention. It is a figure showing the result of the transmission characteristic of Example 1-1 of this invention, and Reference Examples 1-2.

≪Polyarylate resin solution composition≫
The polyarylate resin solution composition of the first aspect of the present invention will be described.
The polyarylate resin solution composition of the present invention comprises a polyarylate resin containing a structural unit containing a dihydric phenol and a structural unit derived from an aromatic dicarboxylic acid, and a solvent.

<Polyarylate resin>
In the present invention, the polyarylate resin includes a structural unit containing a dihydric phenol and a structural unit derived from an aromatic dicarboxylic acid.

[Structural units containing dihydric phenol]
The structural unit containing the dihydric phenol contained in the polyarylate resin contained in the polyarylate resin solution composition in the present invention will be described.
In the present invention, the structural unit containing a dihydric phenol includes a structural unit derived from a compound represented by the following general formula (1).

［式（１）中、Ｒ^１〜Ｒ^４は、互いに独立に、水素原子、炭素数１〜１２の炭化水素基又はハロゲン原子を表す。
Ｒ^５およびＲ^６は、互いに独立に、水素原子又は炭素数１〜４の炭化水素基を表す。
ｍは、４〜７の整数を表す。
Ｘは、炭素原子を表す。
複数の−Ｘ（Ｒ^５）（Ｒ^６）−は、同一であってもよく異なってもよい。］

Wherein ^(1), R 1 ~R ^4, independently of each other, represent a hydrogen atom, a hydrocarbon group or a halogen atom having 1 to 12 carbon atoms.
R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
m represents an integer of 4 to 7.
X represents a carbon atom.
A plurality of —X (R ⁵ ) (R ⁶ ) — may be the same or different. ]

R ^{1 to} R ⁴ independently include a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a halogen, preferably a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, or a phenyl group. And a cyclohexyl group, more preferably a hydrogen atom, a bromine atom, and a methyl group.
Moreover, as R < ⁵ > and R < ⁶ >, a hydrogen atom or a C1-C4 hydrocarbon group is mentioned independently, Preferably hydrogen or a methyl group is mentioned.
When R ¹ , R ² , R ³ and R ⁴ are hydrocarbon groups having 1 to 12 carbon atoms and R ⁵ and R ⁶ are hydrocarbon groups having 1 to 4 carbon atoms, the heat resistance of the polyarylate resin Can be prevented.
m is an integer of 4 to 7, preferably 4 or 5, and more preferably 5.
From the viewpoint of ensuring the stability of the compound represented by the general formula (1) and the viewpoint of ensuring the heat resistance of the resulting polyarylate resin, m is preferably 4 or 5.

  Examples of the compound represented by the general formula (1) include 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane [BisP-TMC], 1,1-bis- (4-hydroxy Phenyl) -3,3,5,5-tetramethyl-cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,4-trimethyl-cyclohexane, 1,1-bis- (4-hydroxyphenyl) ) -3,3-dimethyl-5-ethyl-cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclopentane, 1,1-bis- (3,5-dimethyl) -4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3,5-diphenyl-4-hydroxyphenyl) -3,3,5-trimethyl Cyclohexane, 1,1-bis- (3-methyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3-phenyl-4-hydroxyphenyl) -3,3 , 5-trimethyl-cyclohexane, 1,1-bis- (3,5-dichloro-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3,5-dibromo-4 -Hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3,5-diphenyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3 -Phenyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane Among them, since the high versatility, and the like, preferably a BisP-TMC.

  In this invention, content of the compound shown by General formula (1) is 20 mol% or more with respect to the sum total of all the structural units which comprise polyarylate resin. Further, from the viewpoint of improving solvent solubility, the content of the compound represented by the general formula (1) is preferably 30 mol% or more with respect to the total of all the structural units constituting the polyarylate resin. Preferably it is 35 mol% or more.

  Examples of other dihydric phenol constituting the structural unit containing dihydric phenol include, for example, 2,2-bis (4-hydroxyphenyl) propane [BisA], 2,2-bis (3,5-dimethyl-4-l). Hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) Ethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, bis (3 , 5-Dimethyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ) Hexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) hexane and the like.

  The polyarylate resin solution composition of the present invention contains a constituent unit containing the above-mentioned predetermined dihydric phenol, so that, for example, a laminate for a printed wiring board was produced using the polyarylate resin solution composition of the present invention. In this case, the laminate can have a low dielectric constant and excellent heat resistance.

[Structural units derived from aromatic dicarboxylic acids]
As structural units derived from aromatic dicarboxylic acids,
For example, terephthalic acid, isophthalic acid, diphenyl ether-2,2′-dicarboxylic acid, diphenyl ether-2,3′-dicarboxylic acid, diphenyl ether-2,4′-dicarboxylic acid, diphenyl ether-3,3′-dicarboxylic acid, diphenyl ether- 3,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) alkane diphenate, diphenyl ether-2, 2'-dicarboxylic acid, diphenyl ether-2,3'-dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4, 4'-Zical Phosphate include Configurations units derived from. Among these, since it is highly versatile, it preferably includes a structural unit derived from terephthalic acid and a structural unit derived from isophthalic acid.

  Furthermore, among the above, it is preferable that a structural unit derived from 2,6-naphthalenedicarboxylic acid is included from the viewpoint of suppressing dielectric loss and excellent heat resistance.

In the present invention, the content of structural units derived from 2,6-naphthalenedicarboxylic acid is preferably 10 mol% or more, more preferably 15 mol% or more based on the total of all the structural units constituting the polyarylate resin. It is more preferable that it is 20 mol% or more. Moreover, it is preferable that it is 40 mol% or less with respect to the sum total of all the structural units which comprise polyarylate resin, it is more preferable that it is 30 mol% or less, and it is more preferable that it is 28 mol% or less.
The lower limit value and the upper limit value can be arbitrarily combined. Moreover, when it is below the said lower limit, when the laminated body for printed wiring boards is produced, for example using the polyarylate resin solution composition of this invention, the dielectric constant of this laminated body can be made low.

  The polyarylate resin solution composition of the present invention contains a structural unit derived from the above-mentioned predetermined aromatic dicarboxylic acid, and thus, for example, a laminate for a printed wiring board using the polyarylate resin solution composition of the present invention. When this is manufactured, the laminate can have a low dielectric constant tangent, excellent heat resistance, and a high thermal decomposition temperature.

[Optional ingredients]
In the polyarylate resin, an aliphatic diol such as aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, ethylene glycol, propylene glycol, 1,4-cyclohexanediol, 1,3-cyclohexane, and the like are used as long as the effects of the present invention are not impaired. Alicyclic diols such as cyclohexanediol and 1,2-cyclohexanediol may be copolymerized.

<Solvent>
The polyarylate resin solution composition of the present invention includes a solvent containing a cyclic ketone having 5 to 10 carbon atoms. The “cyclic ketone having 5 to 10 carbon atoms” indicates the total number of carbon atoms including a substituent.
The solvent containing a cyclic ketone is a solvent having a cyclic ketone structure in the molecule, and examples thereof include a solvent having a 5- to 7-membered cyclic ketone structure in the molecule.
Examples of the solvent having a 5-membered cyclic ketone structure in the molecule include cyclopentanone, 2-methyl-2-cyclopenten-1-one, 2-methylcyclopentanone, 3-methylcyclopentanone, 2- Examples include ethylcyclopentanone, 3-ethylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone and the like.
Examples of the solvent having a 6-membered cyclic ketone structure in the molecule include cyclohexanone, 2-cyclohexen-1-one, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2, Examples thereof include 6-dimethylcyclohexanone and 2,2-dimethylcyclohexanone.
Examples of the solvent having a 7-membered cyclic ketone structure in the molecule include cycloheptanone and 2-cyclohepten-1-one.
A polycyclic ketone solvent having a norbornane skeleton or a norbornene skeleton can also be used.
These solvents may be used alone or in combination.

  In the present invention, when a laminate for a printed wiring board is produced using the polyarylate resin solution composition, the cyclic ketone is cyclopentanone from the viewpoint of improving the applicability to the metal layer. Or it is preferable that it is a cyclohexanone.

≪Method for producing polyarylate resin film≫
The manufacturing method of the polyarylate resin film of the 2nd aspect of this invention is demonstrated.
The manufacturing method of the polyarylate resin film of this invention has the process of casting the said polyarylate resin solution composition on a support substrate, and the process of removing a solvent from this solution composition.

[Process of Casting Polyarylate Resin Solution Composition onto Supporting Substrate]
In this step, the polyarylate resin is dissolved in the solvent to prepare a polyarylate resin solution composition, and then the polyarylate resin solution composition is applied to a substrate.

Examples of the substrate include a PET film, a polyimide film, a glass plate, and a stainless plate.
The application method is not particularly limited, for example, wire bar coating, film applicator coating, brush coating or spray coating, gravure roll coating, screen printing, reverse roll coating, lip coating, air knife coating, curtain flow coating, dip coating, etc. A known coating method can be used.

[Step of removing solvent from solution composition]
In this step, the solvent in the polyarylate resin solution composition cast in the above [Step of casting the polyarylate resin solution composition on the support substrate] is evaporated by a method such as heating, decompression, and ventilation. Is preferred.
After this step, the polyarylate resin film can be obtained by peeling the polyarylate resin film from the substrate.

≪Polyarylate resin film≫
A third aspect of the present invention is a polyarylate resin film obtained by the method for producing a polyarylate resin film of the second aspect.
The polyarylate resin film of the present invention is excellent in electrical characteristics when used in a laminate for a printed wiring board.
Since the polyarylate resin film of the present invention contains the predetermined polyarylate resin, for example, when used in an adhesive layer used when producing a laminate for a printed wiring board, the laminate has a dielectric constant. There are excellent effects such as low, low dielectric loss tangent, and high heat resistance.

≪Three layer film≫
The three-layer film according to the fourth aspect of the present invention will be described.
In the three-layer film of the present invention, layers are formed on both sides of a polyimide resin film (hereinafter sometimes referred to as “core layer film”) using the polyarylate resin solution composition, and the core layer film The ratio (T1 / T2) of the thickness (T1) of the layer and the thickness (T2) of the layer formed using the polyarylate resin solution composition is 2 to 20, provided that the two T2s are independent of each other and are the same May be different or different. ).
In the present invention, the same effect can be obtained even when a polyamide resin film or a liquid crystal polymer film is used as the core layer film.
FIG. 1 shows a three-layer film of the present invention. In the three-layer film 20 of FIG. 1, layers 22 a and 22 b formed using the polyarylate resin solution composition are formed on both surfaces of a core layer film 21.

In the present invention, “the thickness of the layer formed using the polyarylate resin solution composition” means the thickness of each layer formed using the polyarylate resin solution composition laminated on both surfaces of the core layer film. Means.
Specifically, it means that each of T2a and T2b in FIG. 1 satisfies T1 and the above-described ratio relationship.

  In the present invention, the thickness (T2) of the layer formed using the polyarylate resin solution composition is such that (T1 / T2) is in the range of 3 to 15 in relation to the thickness (T1) of the core layer film. Is preferable, and it is more preferable that it is in the range of 3.5-10.

In the present invention, as the core layer film, a heat-resistant polyimide film can be suitably used as an electronic material. The said heat resistant polyimide film is not limited, What is formed containing 90 mass% or more of non-thermoplastic polyimides is preferable.
About the said heat resistant polyimide film, it is possible to use the well-known polyimide film marketed, for example. Examples of commercially available polyimide films include “Apical” (manufactured by Kaneka), “Kapton” (manufactured by DuPont, Toray DuPont), “Iupilex” (manufactured by Ube Industries), and the like. You may use the heat resistant polyimide film suitably produced using the conventionally well-known raw material or a manufacturing method. For example, the aromatic tetracarboxylic dianhydride and the aromatic diamine are usually dissolved in an organic solvent in a substantially equimolar amount, and the aromatic tetracarboxylic dianhydride is controlled under controlled temperature conditions. The polyamic acid varnish as a precursor is produced by stirring until the polymerization of the diamine with the aromatic diamine is completed, and a heat-resistant polyimide film can be obtained using the polyamic acid varnish.

In the three-layer film of the present invention, the thicknesses of the layers formed using the polyarylate resin solution composition (T2a and T2b in FIG. 1) are independent of each other and may be the same or different. . In the present invention, it is preferable that they are the same. However, the effects of the present invention can be obtained, and further adjustment and change can be made as appropriate as long as the warp does not cause a practical problem when a three-layer film is formed. it can.
For example, when the core layer film has a hardness that can prevent warping, even if a difference is provided in the thickness (T2a and T2b in FIG. 1) of the layer formed using the polyarylate resin solution composition. Good.
When the thickness of layers formed using the polyarylate resin solution composition (T2a and T2b in FIG. 1) is different, for example, the difference between the thickness of T2a and the thickness of T2b should be within ± 25%. Is preferable, within ± 15%, more preferably within ± 10%.

  The polyarylate resin solution composition of the present invention is excellent in low dielectric constant, high heat resistance, and solvent solubility. For this reason, when the three-layer film which formed the polyarylate resin solution composition of this invention on both surfaces of the core film layer was used for the printed circuit board etc., it can be set as the thing excellent in the electrical property.

As a laminate in which the three-layer film of the present invention can be suitably used, for example, as shown in FIG. 2, a laminate in which metal layers 30a and 30b are laminated on both surfaces of the three-layer film 20 of the present invention can be mentioned.
The metal layer is preferably copper, aluminum, silver or an alloy containing one or more metals selected from these. Among these, copper or a copper alloy is preferable because it has more excellent conductivity. The metal layer is preferably made of a metal foil, more preferably a copper foil, because the material is easy to handle, can be easily formed, and is excellent in economy. When providing a metal layer on both surfaces of a three-layer film, the material of these metal layers may be the same and may differ.
The thickness of a metal layer becomes like this. Preferably it is 1-50 micrometers, More preferably, it is 3-35 micrometers, More preferably, it is 5-20 micrometers.

Below, the manufacturing method of the three-layer film of this invention is demonstrated.
<Three-layer film production method 1>
In the present invention, the three-layer film comprises a liquid composition coating step in which the polyarylate resin solution composition is coated on the core layer film, and the core layer film is covered with the solution composition; and the solvent in the solution composition It can manufacture by the solvent removal process which removes, and a heat processing process.

[Liquid composition coating process]
The manufacturing method of the three-layer film of this invention has the solution composition application | coating process which apply | coats the said polyarylate resin solution composition on a core layer film, and covers the said core layer film with the said solution composition.
The description regarding the polyarylate resin solution composition and the core layer film is the same as the description in the three-layer film of the present invention.
Examples of the method for applying the solution composition onto the core layer film include various means such as roller coating, dip coating, spray coating, curtain coating, slot coating, and screen printing.

  In this invention, a solution composition is apply | coated to both surfaces of a core layer film with said application | coating method. At this time, the thickness of the polyarylate resin can be adjusted by the coating amount of the liquid composition.

[Solvent removal step]
After the [solution composition coating step], the solvent in the polyarylate resin solution composition is removed.
Here, the method for removing the solvent is not particularly limited, but it is preferably performed by evaporation of the solvent. Examples of the method for evaporating the solvent include methods such as heating, reduced pressure, and ventilation. Among them, heating and evaporation are preferable from the viewpoints of production efficiency and handleability, and heating and evaporation can be performed while ventilating. More preferred.
The heat treatment in the solvent removal step may be appropriately selected depending on the solvent applied to the solution composition, may be heat-treated at 60 to 200 ° C. for 60 to 600 seconds, and preferably 120 to 600 seconds. By setting it as more than a lower limit, a solvent is fully removed and blocking is suppressed in the obtained three-layer film.
Further, the removal of the solvent in the [solvent removal step] is not necessarily complete, and the remaining solvent may be removed in the next [heat treatment step]. From the viewpoint of preventing the surface roughness of the polyarylate resin layer, it is preferable to remove the solvent by this [solvent removal step].

[Heat treatment process]
After the [solvent removing step], heat treatment is performed. As the heat treatment, for example, a method of heating by heating the three-layer film under an inert gas atmosphere can be employed. What is necessary is just to adjust heat processing conditions suitably with the employ | adopted liquid composition, for example, may be performed in the range of 250 to 400 degreeC for 1 minute to 4 hours.

  In the manufacturing method 1 of a three-layer film, first, a solution composition is apply | coated to the single side | surface of a core layer film, and the solvent in the said solution composition is removed. Next, this operation is repeated on the other surface, and finally the heat treatment is performed, whereby the three-layer film of the first aspect of the present invention can be obtained.

<Method 3 for producing a three-layer film>
A three-layer film may be manufactured by the manufacturing method 2 of the three-layer film including an impregnation process.
The three-layer film production method 2 includes an impregnation step of impregnating a core layer film in a polyarylate resin solution composition and covering the core layer film with the solution composition, and a solvent for removing the solvent in the solution composition It is a manufacturing method including a removal step and a heat treatment step.

[Impregnation process]
In the impregnation step, the core layer film is impregnated in the polyarylate resin solution composition.
The description regarding the polyarylate resin solution composition and the core layer film is the same as the description in the three-layer film of the present invention.
After the impregnation step, the core layer film impregnated with the solution composition is passed between a pair of rolls whose interval is narrower than its thickness. By this step, the solution composition excessively attached to the surface of the core layer film can be removed.

FIG. 3 is a schematic view for explaining a method of continuously performing an impregnation step and a roll passage step using a long core layer film. However, what is shown here is an example, and the impregnation step in the present invention is not limited to the one shown here.
The core layer film 10 is induced by the guide roller 4 and the guide rollers G ₁ moves in the arrow direction, is dipped in the liquid composition W immersion tank 3, then the core layer film 11 immediately after the solution composition impregnated, It is pulled up from the immersion tank 3 and sent to a squeeze roll 5 having a pair of rolls 5A and 5B. The pair of rolls 5A and 5B are arranged to face each other so as to sandwich the core layer film 11, and the distance between them is at least the thickness of the core layer film 11 (the core layer film 10 and the solution composition W impregnated therein). Is adjusted to be narrower than the total thickness including). The core layer film 11 is squeezed by passing between such a pair of rolls 5A and 5B so that an excess solution composition is removed and the solution composition is sufficiently impregnated inside. The impregnated core layer film 12 is obtained.

  The pair of rolls 5 </ b> A and 5 </ b> B may rotate (self-rotate) themselves, or may rotate with the traveling of the core layer film 11 immediately after impregnation with the solution composition. When the pair of rolls 5A and 5B are self-rotating, the amount of the solution composition attached to the solution composition-impregnated core layer film 12 can be easily adjusted, and the target liquid composition-impregnated core layer film The surface is also sufficiently smoothed and the smoothness of the surface is improved.

  The film thickness of the polyarylate resin layer is adjusted to the desired film thickness by adjusting the pulling speed from the dipping tank 3 and the distance between the pair of rolls 5A and 5B in the squeeze roll 5. be able to.

The explanation regarding the [solvent removal step] and the [heating step] in the production method 2 of the three-layer film is the same as the explanation in the production method 1 of the three-layer film.
Specifically, as the [solvent removing step], the solution composition-impregnated core layer film that has passed between the rolls 5A and 5B may be heat-treated at 60 to 200 ° C. for 60 to 600 seconds, and for 120 to 600 seconds. Preferably there is.
By this heat treatment, the solvent of the solution composition impregnated in the solution composition-impregnated core layer film is removed by evaporation, and the intended three-layer film is obtained.
And as a [heating process], what is necessary is just to heat-process in the range of 250 to 400 degreeC for 1 minute to 4 hours, for example. By setting the temperature and time of the heat treatment in this way, a three-layer film with reduced voids can be stably obtained.

≪Three-layer film manufacturing method 3≫
A three-layer film may be manufactured by the manufacturing method 3 of a three-layer film.
In the manufacturing method 3 of a three-layer film, a polyarylate resin solution composition is first apply | coated to a support body shape, and the solvent in the said solution composition is removed. Next, the core layer film-forming resin composition is applied, and the solvent of the core layer film-forming resin liquid composition is removed. Furthermore, a polyarylate resin solution composition is applied, and the solvent in the solution composition is removed. Finally, a three-layer film can be obtained by heat treatment and peeling from the support.
Moreover, in the manufacturing method 3 of a three-layer film, a polyarylate resin solution composition, a core film-forming resin composition, and a polyarylate resin solution composition are applied in this order to a support, and the solution composition contains Remove the solvent. Finally, a three-layer film may be obtained by heat treatment and peeling from the support.

≪Laminated board≫
A fifth aspect of the present invention is a laminated board characterized in that the three-layer film obtained by the fourth aspect is used as an insulating layer, and a metal layer is formed on at least one surface of the insulating layer. is there.
In the laminate of the present invention, it is sufficient that a metal layer is formed on at least one side of the three-layer film, but it is preferable that metal layers are laminated on both sides. More specifically, the laminate shown in FIG. 2 is a laminate in which metal layers are laminated on both surfaces of the three-layer film, and 30a and 30b in FIG. 2 are laminates.

The metal layer laminated | stacked on the said three-layer film is demonstrated.
The metal layer in the laminated board of the present invention is a copper foil having a tensile modulus after heat treatment at 300 ° C. of 60 GPa or less and a stress at break of 150 MPa or less. The lower limit related to the tensile modulus is 10 GPa or more in a practical range, and preferably 20 GPa or more. The lower limit related to the stress at break is preferably 20 MPa or more and particularly preferably 30 MPa or more in a practical range.
The type of metal layer used in the present invention may be either a layer formed by electrolysis or a layer formed by rolling. In order to obtain a copper foil as an example of a metal layer having the above characteristics, Is a technique defined by JIS C2151 from high temperature elongation (high temperature high elongation copper foil, hereinafter referred to as “HTE copper foil”) and a rolled copper foil, which are well known in the art. The tensile modulus and stress at break can be determined and selected.

The thickness of the metal layer used in the laminate of the present invention is preferably in the range of more than 5 μm and not more than 35 μm, more preferably in the range of 9 to 28 μm. When the thickness of the metal layer is within the above range, it is preferable that the tension of the metal layer can be easily adjusted at the time of manufacturing the laminate, and the flexibility of the resulting laminate is further improved.
In the laminated plate, the maximum height (Rz) of the metal layer is preferably in the range of 0.5 to 2.5 μm, more preferably in the range of 0.6 to 2.4 μm, and 0.6 to The range of 2.2 μm is particularly preferable.

Specific examples of preferred metal layers for use in the present invention are given below. As the metal layer, a metal layer made of a metal containing copper is preferable.
Specifically, a copper foil is preferable as the metal layer. Among them, as the HTE copper foil, for example, SQ-HTE copper foil (manufactured by Mitsui Metal Mining Co., Ltd.), 3EC-M3S-HTE copper foil (manufactured by Mitsui Metal Mining Co., Ltd.), NS -HTE copper foil (manufactured by Mitsui Kinzoku Mining Co., Ltd.), 3EC-HTE copper foil (manufactured by Mitsui Kinzoku Mining Co., Ltd.), F2-WS copper foil (manufactured by Furukawa Electric Co., Ltd.), HLB (manufactured by Nippon Electrolytic Co., Ltd.), CF-T4X-DS -SVR (manufactured by Fukuda Metal Foil Powder Co., Ltd.) and the like, and as rolled copper foil, for example, RCF-T5B-HPC (manufactured by Fukuda Metal Foil Powder Co., Ltd.), BHY-22B-T (manufactured by JX Nippon Mining & Metals) BHY-22B-HA (manufactured by JX Nippon Mining & Metals), BHYA-T (manufactured by JX Nippon Mining & Metals), BHYA-HA (manufactured by JX Nippon Mining & Metals) and the like. These copper foils are readily available from the market.

  By using the copper foil having the above characteristics for the laminate of the present invention, a laminate having excellent adhesion between the metal layer and the resin layer and excellent flexibility and folding resistance can be realized.

As a method for integrating the three-layer film and the metal layer, a method of hot pressing the metal layer and the three-layer film is preferably used. For example, a method of performing hot pressing by holding at a pressure of 200 to 350 ° C. and a pressure of 3 to 10 MPa for 10 to 60 minutes using a conventional press machine can be mentioned.
The liquid crystal polymer laminate of the present invention thus obtained is a multilayer printed circuit board for a semiconductor package or a mother board obtained by a build-up method or the like that has been attracting attention in recent years due to excellent characteristics such as dimensional stability and low hygroscopicity. It is suitably used for flexible printed wiring boards, tape automated bonding films, and the like.

<Printed circuit board>
A sixth aspect of the present invention is a printed circuit board using the three-layer film as an insulating layer. The printed circuit board of the present invention can have the same configuration as a known printed circuit board except that the three-layer film is used as an insulating layer, and can be manufactured by the same method.

  In the printed circuit board of the present invention, for example, a metal layer is provided on one side or both sides of an insulating layer made of a single three-layer film or an insulating layer formed by laminating a plurality of the three-layer films. A laminated body is produced, a predetermined circuit pattern is formed on the metal layer of the laminated body by etching or the like, and the laminated body on which this circuit pattern is formed is laminated as it is or as needed, Can be manufactured. The printed circuit board of the present invention is preferably one in which metal layers are laminated on both sides of a three-layer film.

  In the case of an insulating layer in which a plurality of the three-layer films are laminated, the plurality of three-layer films may all be the same, only a part may be the same, or all may be different. The number of sheets is not particularly limited as long as it is two or more. Such an insulating layer can be produced, for example, by laminating a plurality of three-layer films in the thickness direction, heat-pressing and fusing them together.

The material of the metal layer is preferably copper, aluminum, silver or an alloy containing one or more metals selected from these. Of these, copper or a copper alloy is preferable from the viewpoint of having superior conductivity. The metal layer is preferably made of a metal foil, more preferably a copper foil, because the material is easy to handle, can be easily formed, and is excellent in economy. When providing a metal layer on both surfaces of an insulating layer, the material of these metal layers may be the same and may differ.
The thickness of a metal layer becomes like this. Preferably it is 1-50 micrometers, More preferably, it is 3-35 micrometers, More preferably, it is 5-20 micrometers.

  As a method of providing a metal layer, a method of fusing a metal foil to the surface of the insulating layer, a method of adhering the metal foil to the surface of the insulating layer with an adhesive, a plating method, a screen printing method or a sputtering method on the surface of the insulating layer Can be exemplified by a method of coating with metal powder or metal particles.

  When the insulating layer is formed by laminating a plurality of the three-layer films, the three-layer films are arranged in the thickness direction, and the surface of one or both of the three-layer films located on the outermost side is arranged. In addition, when the insulating layer is formed by further pressing the metal foil and pressing the metal foil and the plurality of three-layer films, the metal layer can be simultaneously provided on one side or both sides of the insulating layer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.

[Example 1]
Into a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 124.2 g of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (0. 40 mol), 2,2-bis (4-hydroxyphenyl) propane 22.8 g (0.10 mol), isophthalic acid 41.5 g (0.25 mol), 2,6-naphthalenedicarboxylic acid 54.0 g (0 .25 moles) and 112.3 g (1.1 moles) of acetic anhydride.
After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen gas stream, and the temperature was maintained and refluxed for 3 hours.
Thereafter, the temperature was raised to 310 ° C. over 170 minutes while distilling off the by-product acetic acid and unreacted acetic anhydride, and the time when an increase in torque was observed was regarded as the completion of the reaction, and the contents were taken out. The obtained solid content was cooled to room temperature, pulverized with a coarse pulverizer, held at 290 ° C. for 5 hours in a nitrogen atmosphere, and the polymerization reaction proceeded in a solid phase.

  100 g of the obtained polyarylate resin powder was added to 900 g of cyclohexanone, heated to 100 ° C. and completely dissolved to obtain a yellow transparent polyarylate resin solution composition having a solid content of 10 wt%. Next, on the polyimide resin film (Kapton (registered trademark) 150EN, manufactured by Toray DuPont Co., Ltd.), using the film applicator so that the final thickness is 6 to 7 um, the obtained solution composition is obtained at room temperature. After casting, the solvent was removed by heating at 100 ° C. for 10 minutes using a high-temperature hot air dryer to obtain a coating film.

[Example 2]
100 g of the polyarylate resin powder obtained in Example 1 was added to 900 g of cyclopentanone, heated to 100 ° C. and completely dissolved to obtain a yellow transparent polyarylate resin solution composition having a solid content of 10 wt%. Coating was performed in the same manner as in Example 1 using the obtained solution composition.

[Comparative Example 1]
The same operation as in Example 1 was performed except that NMP was used as the solvent for dissolving the polyarylate resin powder obtained in Example 1.

[Comparative Example 2]
The same operation as in Example 1 was performed except that DMAc was used as the solvent for dissolving the polyarylate resin powder obtained in Example 1.

[Comparative Example 3]
The same operation as in Example 1 was performed except that the solvent for dissolving the polyarylate resin powder obtained in Example 1 was changed to THF.

[Comparative Example 4]
The same operation as in Example 1 was performed except that toluene was used as a solvent for dissolving the polyarylate resin powder obtained in Example 1.

[Comparative Example 5]
The same operation as in Example 1 was performed except that 1,3-dioxolane was used as the solvent for dissolving the polyarylate resin powder obtained in Example 1.

Table 1 shows the results of evaluating the coating properties, drying properties, and appearance after drying of the solution compositions used in each Example and Comparative Example.
[Applicability]
Immediately after casting the polyarylate resin solution composition using a film applicator, whitening or uneven coating occurs “x” (determined as defective), and “○” (good) when none is visible Judgment).
[Drying]
When the polyarylate resin solution composition cast on polyimide is heated at 100 ° C. for 10 minutes using a high temperature hot air dryer to remove the solvent, the tackiness of the coating film remains, or uneven film thickness occurs. “X” (determined as defective), and “O” (determined as good) when the appearance was good without any phenomenon.
[Appearance after drying]
Applicability and drying properties are both good, and when the solvent does not bleed after drying, “○” (determined as good), and any one of the coating properties, drying properties, and solvent leaching after drying. The case where it was defective was defined as “x” (determined as defective).

In Examples 1 and 2, it was found that the coating property, drying property, and appearance after drying were all good, and that the polyimide resin film exhibited high adhesion.
In Comparative Examples 1 and 2, the coating properties were good, but the drying properties were poor, resulting in film thickness unevenness and insufficient drying. In Comparative Examples 3 to 5, whitening or coating unevenness occurred immediately after coating.

<Circuit pattern formation>
[Example 1-1]
The polyarylate resin solution composition obtained in Example 1 was placed on one side using a film applicator (coating thickness 70 μm) on Kapton 150EN (manufactured by Toray DuPont) having a film thickness of 37.5 μm, which is a commercially available polyimide resin film. Apply, heat at 100 ° C. with a hot air dryer to remove the solvent, repeat this operation on the other side, heat treatment at 350 ° C. with a high temperature hot air dryer to form a three-layer film (polyarylate resin). Layer / polyimide resin film / polyarylate resin = 6.25 μm / 37.5 μm / 6.25 μm).
The three-layer film obtained above was used as an insulating layer, and copper foil (“BHY-22B-T” (thickness 18 μm, Rz = 0.7 μm) manufactured by JX Nippon Mining & Metals) was laminated on both sides thereof. . This is hot-pressed and integrated for 20 minutes at a temperature of 340 ° C. and a pressure of 5 MPa with a high-temperature vacuum press (“KVHC-PRESS” manufactured by Kitagawa Seiki Co., Ltd., length 300 mm, width 300 mm). A double-sided copper-clad laminate was obtained.

[Reference Example 1]
A double-sided copper clad laminate (“R-F075T” manufactured by Panasonic Corporation) in which a copper foil was laminated on both sides of the liquid crystal polymer film was used.

[Reference Example 2]
A double-sided copper-clad laminate (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “Espanex SB-18-50-18FR”) in which a copper foil was laminated on both sides of the polyimide resin film was used.

  About the double-sided copper-clad laminate obtained above, TDR measurement was performed to produce a printed circuit board so as to have a resistance of 100Ω. Formed.

<Transmission loss measurement>
About the printed circuit pattern in which the circuit pattern was formed, the transmission loss (SDD21 parameter) was measured using the measurement probe “E8363B” manufactured by Arranged Technology. The result is shown in FIG.

As shown in FIG. 4, the double-sided copper-clad laminate of Example 1-1 formed using the polyarylate resin solution composition of Example 1 has a low rate of change in transmission loss and is equivalent to or equal to that of Reference Example 1. The result became lower than above.
In contrast, Reference Example 2 had a very high rate of change in transmission loss.

DESCRIPTION OF SYMBOLS 20 ... Three-layer film, 21 ... Polyimide resin film, 22a, 22b ... Liquid crystal polymer layer, 30a, 30b ... Metal layer, 3 ... Dipping tank, 4 ... Guide roller, 5 ... squeeze roll, 5A, 5B ... roll, 10 ... polyimide resin film, 11 ... polyimide resin film immediately after impregnation with liquid composition, 12 ... liquid composition impregnation polyimide resin film, W ..Liquid composition, G ₁ ... guide roller

Claims (10)

A structural unit containing a dihydric phenol, and a structural unit derived from an aromatic dicarboxylic acid,
Polyarylate resin, including
As well as a solvent,
The polyarylate resin is a structural unit containing a dihydric phenol, and the structural unit derived from a compound represented by the following general formula (1) is the total of all the structural units constituting the polyarylate resin. , 20 mol% or more,
A polyarylate resin solution composition comprising a cyclic ketone having 5 to 10 carbon atoms as the solvent.

Wherein ^(1), R 1 ~R ^4, independently of each other, represent a hydrogen atom, a hydrocarbon group or a halogen atom having 1 to 12 carbon atoms.
R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
m represents an integer of 4 to 7.
X represents a carbon atom.
A plurality of —X (R ⁵ ) (R ⁶ ) — may be the same or different. ]   The polyarylate resin solution composition according to claim 1, wherein the solvent is cyclopentanone or cyclohexanone.   The polyarylate resin solution composition according to claim 1 or 2, wherein the compound represented by the general formula (1) is 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.   The polyarylate resin solution composition according to any one of claims 1 to 3, wherein the structural unit derived from an aromatic dicarboxylic acid includes a structural unit derived from 2,6-naphthalenedicarboxylic acid. A step of casting the polyarylate resin solution composition according to any one of claims 1 to 4 on a support substrate;
A process for removing the solvent from the solution composition, and a method for producing a polyarylate resin film.   A polyarylate resin film obtained by the method for producing a polyarylate resin film according to claim 5.   A layer is formed on both surfaces of the polyimide resin film using the polyarylate resin solution composition according to any one of claims 1 to 4, and the thickness (T1) of the polyimide resin film and the polyarylate resin solution composition A three-layer film characterized in that the ratio (T1 / T2) of the thickness (T2) of layers formed using a material is 2 to 20 (provided that the two T2s are independent of each other and are the same) Well, it can be different.)   A laminate comprising a metal layer formed on at least one side of the three-layer film according to claim 7.   The laminate according to claim 8, wherein the metal layer contains copper.   A printed circuit board using the laminate according to claim 8.

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