JP2002356544A - Low-dielectric electronic material and resin composition for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-dielectric electronic material having an excellent low-dielectric property with processability required for an electronic material, a sheet and laminated board composed of the material, and a production method of a polyarylate having the low-dielectric property used as the material. SOLUTION: The low-dielectric electronic material comprises the polyarylate which consists of a residue of a dicarboxylic acid such as isophthalic acid and a residue of a dihydric phenol having a fluorene structure without having a bisphenol structure and/or an alkyl group and has a dielectric coefficient of below 2.0×10<-3> at 1 GHz. The production method of the same, a resin composition for an electronic material comprising the polyarylate and a thermosetting resin such as an epoxy resin with a compound having an active ester group as a curing agent, the low-dielectric electric materials comprising these resin compositions for an electric material and the sheet and laminated board comprising these low-dielectric electronic materials, are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low dielectric electronic material comprising a polyarylate having an excellent low dielectric loss tangent, which is useful as an electronic material such as an insulating sheet and a printed wiring board material for high frequencies. The present invention relates to a low dielectric electronic material made of a specific thermosetting resin, a laminate having a sheet and a metal foil made of the same, and a method for producing a polyarylate.

[0002]

2. Description of the Related Art In the recent information society, in order to transmit and process an enormous amount of information, a high frequency band in a MHz to GHz band has been used for information communication. Therefore, suppression of transmission loss, that is, low dielectric loss tangent of an insulator is very important, and an electronic material having an extremely low dielectric loss tangent of 2.0 × 10 ⁻³ or less at 1 GHz is required.

Further, since these are used as a laminate such as a printed wiring board, they are also required to have excellent mechanical properties and high heat resistance capable of withstanding the heat of soldering during processing.
To meet these demands, polyarylate, a condensation polymer of dihydric phenol and isophthalic acid / terephthalic acid, has been attracting attention as an electronic material because of its excellent mechanical properties, isotropic properties and electrical properties, Many reports have been made.

For example, JP-A-58-180525 discloses a polyarylate having a biphenol structure, which is one of the polyarylates used for the low dielectric electronic material of the present invention, a general production method of the polyarylate, and A film comprising the same is disclosed.

JP-A-10-17658 discloses that polyarylate having a biphenol structure used in the present invention is polycondensed with a dicarboxylic acid together with a dihydric phenol containing an aliphatic chain in a main chain such as bisphenol A. The dielectric constant and the dielectric loss tangent of the allylate at 1 MHz are 3.1
And 1.82 × 10 ⁻² .

JP-A-57-192432 discloses that the polyarylate having a biphenol structure having a fluorene skeleton used in the present invention has a dielectric loss tangent and a dielectric constant at 1.0 KHz of 3.0 × 10 ⁻³ and 3.0 × 10 ⁻³ , respectively. 3, which is disclosed as a polyarylate having excellent electrical properties.
These have a specific structure of the present invention and, unlike polyarylate purified by a specific method, show a low dielectric loss tangent that is two or one orders of magnitude lower.

Further, Japanese Patent Application Laid-Open No. 10-306146 and Japanese Patent Application No. 2000-053373 by the present inventors disclose:
When obtaining a polyarylate having a biphenol structure used in the present invention, a method of precipitating the polyarylate by passing a solution containing the polyarylate through a poor solvent is disclosed, as shown in Comparative Examples of the present invention. Subsequent purification of the precipitate by washing was not performed, and the dielectric loss tangent did not reach an extremely high level of the object of the present invention, ie, 2.0 × 10 ⁻³ or less at 1 GHz.

On the other hand, WO 99/18141 discloses a novel polyarylate in which the dihydric phenol component is a fluorene residue having an alkyl substituent, the carboxyl value of which is 30 mol / ton or less, and the remaining alkali. A highly heat-resistant and high-purity polyarylate having a metal content of less than 50 ppm, a residual catalyst of less than 200 ppm, and a residual phenol monomer and dicarboxylic acid content of 1000 ppm or less, respectively, and a film comprising the same are disclosed. Excellent heat resistance and low birefringence are disclosed with data.

However, the publication does not disclose at all what electrical properties these novel polyarylates have. In addition, although the carboxyl number of the novel polyarylate, the amount of the remaining alkali metal, the amount of the remaining catalyst and the remaining phenol monomer and dicarboxylic acid exceed the above-mentioned values, there is a description that the electrical properties tend to decrease, Does not disclose how any electrical property is degraded when the numerical value exceeds the above-mentioned numerical value.

[0010] Further, Japanese Patent Application Laid-Open No. 2000-2 by the present inventors.
No. 73297 describes a resin composition of a polyarylate having a biphenol skeleton and an epoxy resin, but the exemplified use of the epoxy resin composition is mainly for a paint, and a curing agent for the epoxy resin is generally used. An acid anhydride, an amine, a phenol, and a mercaptan-based epoxy resin composition. As shown in Comparative Examples of the present invention, no excellent low dielectric loss tangent was obtained with this epoxy resin composition.

[0011]

The problem to be solved by the present invention is to provide an extremely low dielectric constant having a dielectric loss tangent at 1 GHz of 3.0 × 10 ^-3 or less, which has not been achieved before. A low-dielectric electronic material having both heat resistance, mechanical properties such as tensile strength, and workability required for an electronic material such as easy adjustment of solvent solubility and solution viscosity, and the like. An object of the present invention is to provide a sheet and a laminate, and a method for producing a polyarylate having low dielectric properties used for the low dielectric electronic material.

[0012]

The present inventors have conducted intensive studies and have found that a specific bisphenol structure and / or a dihydric phenol having at least one of a fluorene structure having no alkyl substituent and phthalic acid, isophthalic acid and terephthalic acid. A polyarylate obtained by interfacial polycondensation with a dicarboxylic acid selected from the group consisting of acids and having a proportion of terephthalic acid of 40 mol% or less of the total dicarboxylic acid is precipitated as a fine precipitate with a poor solvent, and then hydrophilically precipitated. The present inventors have found that a polyarylate having an extremely low dielectric loss tangent can be obtained by washing and purifying the precipitate with a neutral solvent, thereby completing the present invention.

That is, the present invention comprises a repeating unit (-(A)-(B)-) of the structural units (A) and (B), wherein the structural unit (A) is phthalic acid, isophthalic acid and terephthalic acid. And the proportion of terephthalic acid residues in the residues of the dicarboxylic acid is 40 mol% or less, and the structural unit (B) is represented by the general formula (I):

[0014]

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(Wherein Q and R each have 1 to 1 carbon atoms)
An alkyl group of 4 and m and n each represent an integer of 0 to 4);

[0016]

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Wherein the total content of alkali metal, alkaline earth metal and free halogen is 250 ppm or less and the dielectric loss tangent at 1 GHz is 2.0 × Provided is a low dielectric electronic material comprising polyarylate (C) having a density of 10 ⁻³ or less.

The present invention comprises repeating units (-(A)-(B)-) of the structural units (A) and (B), wherein the structural unit (A) comprises phthalic acid, isophthalic acid and terephthalic acid. A residue of a dicarboxylic acid selected from the group, the proportion of terephthalic acid residues in the residue of the dicarboxylic acid is 40 mol% or less, and the structural unit (B) is represented by the general formula (I)

[0019]

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(Wherein Q and R each have 1 to 1 carbon atoms)
An alkyl group of 4 and m and n each represent an integer of 0 to 4);

[0021]

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A polyarylate (C) comprising at least one dihydric phenol residue, an epoxy resin, a diallyl phthalate resin, a bismaleimide-triazine resin, a vinyl benzyl ether-based resin, and an isocyanurate-based resin A resin, a benzodiclobutene-based resin, a divinylbenzene-based resin, and one or more thermosetting resins (D) selected from the group consisting of polybutadiene-based resins;
Provided is a resin composition for electronic materials, wherein the content of alkali metal, alkaline earth metal and free halogen is 250 ppm or less.

The present invention also provides a resin composition for electronic materials wherein the above-mentioned polyarylate (C) and thermosetting resin (D) are epoxy resins, wherein the epoxy resin has a general formula (III)

[0024]

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Wherein k is an integer of 2 to 4, and R ¹ is

[0026]

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Any aromatic ring of the formula (wherein S, T,
U, V and W are each an alkyl group having 1 to 4 carbon atoms, o
And t are each an integer of 0 to 5, q and r are each an integer of 0 to 4, p is an integer of 0 to 3), and R ² is

[0028]

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The present invention provides a resin composition for an electronic material, which comprises an aromatic ester represented by any one of the above (2) and (3) in combination with the epoxy resin.

The present invention also relates to a sheet made of a low dielectric electronic material comprising the polyarylate (C), a sheet with a metal foil having a metal foil on one or both sides of the sheet, or a thermoset with the polyarylate (C). Resin composition for electronic materials, comprising a reactive resin (D) and having an alkali metal, alkaline earth metal and free halogen content of 250 ppm or less, and 1 GH obtained by curing the electronic material resin composition.
A low-dielectric electronic material having a dielectric loss tangent at z of 3.0 × 10 ⁻³ or less, a sheet made of a semi-cured product of the resin composition for electronic material, or one or both surfaces of a sheet made of the semi-cured material A sheet with a metal foil having a metal foil, a sheet made of a low-dielectric material made of the polyarylate (C), a sheet made of a semi-cured product of the resin composition for an electronic material, and a sheet made of these metal foils The above provides a laminated plate formed by heating and pressing.

The present invention also relates to a dicarboxylic acid halide (A ') selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid, wherein the proportion of terephthalic acid is not more than 40 mol% of the total dicarboxylic acid. Formula (IV)

[0032]

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(Wherein Q and R each have 1 to 1 carbon atoms)
An alkyl group of 4, m and n each represent an integer of 0 to 4) and a general formula (V)

[0034]

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An organic solvent solution of polyarylate obtained by interfacial polycondensation with any one or more dihydric phenol compounds (B ') is brought into contact with a poor solvent of polyarylate, and Get a fine precipitate,
Next, the fine precipitate of the polyarylate is washed with at least one of water and a hydrophilic solvent, wherein the total content of alkali metals, alkaline earth metals and free halogens is 250 ppm or less and the dielectric loss tangent at 1 GHz. Is 2.0 × 10 ⁻³ or less.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, the polyarylate having a specific structure used in the present invention will be described. The polyarylate used in the present invention is composed of repeating units (-(A)-(B)-). The structural unit (A) is a residue of a dicarboxylic acid selected from phthalic acid, isophthalic acid, and terephthalic acid, and the proportion of the terephthalic acid residue in the dicarboxylic acid residue is 40 mol% or less.

When the proportion of terephthalic acid residues exceeds 40 mol%, the proportion of aromatic rings connected at the para-position in the polyarylate molecular chain increases, and the molecular chain becomes rigid instead of flexible. , NMP or other organic solvents having a high dissolving power cannot be obtained. In particular, the structural unit (A) is composed of only an isophthaloyl group / terephthaloyl group, and the molar ratio thereof is 61/39 to 95/5, particularly 72/2.
5 to 84/16) is preferable in order to achieve both heat resistance and solubility in an organic solvent.

For example, when the structural unit (B) is 3, 3 ', 5,
In the case of a 5′-tetramethylbiphenol residue, chloroform, methylene chloride, and the like, if the molar ratio of isophthalic acid residue / terephthalic acid residue in the structural unit (A) is in the range of 75/25 to 84/16, It can be dissolved in solvents such as tetrachloroethane, chlorobenzene, tetrahydrofuran, dioxolane, N-methylpyrrolidinone (NMP), and anisole at a concentration of 5% by weight or more. It has favorable processability in producing the composition.

Next, the structural unit (B) will be described. The structural unit (B) has the general formula (I)

[0040]

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(Wherein Q and R each have 1 to 1 carbon atoms)
An alkyl group of 4, m and n each represent an integer of 0 to 4), and a dihydric phenol having a bisphenol structure
And general formula (II)

[0042]

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Any one or more of dihydric phenols having a fluorene structure having no alkyl substituent represented by
It is a phenol residue.

In the case of a dihydric phenol residue having a biphenol structure, the alkyl groups having 1 to 4 carbon atoms for Q and R are each independently a linear or chain alkyl group. , A methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a sec-butyl group or an n-butyl group.

Particularly, Q and R are preferably a methyl group, and m and n are each preferably 2. When the substitution position is 3,3 ', 5,5', it is more preferable to exhibit flame retardancy.
Most preferably, it is a 3 ', 5,5'-tetramethylbiphenol residue. In addition, 2 having a fluorene structure
In the case of a divalent phenol, it is preferable that the fluorene structure has no alkyl substituent from the viewpoint of suppressing the dielectric loss tangent.

As the above-mentioned dihydric phenol, a dihydric phenol having a biphenyl skeleton represented by the general formula (I) has a low dielectric loss tangent and excellent organic solvent solubility, and removes impurities such as alkali metals by washing described later. Is particularly preferable from the viewpoint of obtaining a polyarylate having excellent workability and dielectric properties.

The ratio of the structural unit (A) to the structural unit (B) is not particularly limited as long as the effect of the present invention is achieved, but the molar ratio of (A) / (B) is 0.8. To 1.2, more preferably 0.9 to 1.1 in order to obtain a molecular weight showing sufficient mechanical strength.

The polyarylate (C) used in the present invention is a flexible polymer having a specific structure and is advantageous over other polyarylates in that it can be formed into a thin film from a state dissolved in an organic solvent. Unlike a rigid liquid crystal polyarylate that melts, it does not undergo flow deformation even when immersed in a solder bath at 260 to 320 ° C. Further, the polyarylate used in the present invention also has an advantage in that the anisotropy of the characteristic manifestation, which is a practically significant problem in liquid crystal polyarylate, is suppressed.

The molecular weight of the polyarylate (C) is not particularly limited, but is preferably in an appropriate molecular weight range in order to obtain mechanical strength, solubility in a solvent and coatability of a solution.
Specifically, the inherent viscosity value in the chloroform solution is preferably 0.6 to 3.2 dL / g, and
0 to 2.6 dL / g is more preferred.

In particular, when the polyarylate (C) is used in the form of a composition with the thermosetting resin (D) to be described later, the inherent viscosity is 2.0 to obtain excellent toughness.
It is preferably ~ 2.6 dL /. When the inherent viscosity is 0.6 dL / g or more, improvement in mechanical strength, chemical stability and sufficient heat resistance can be obtained. 3.2d
L / g or less is advantageous in terms of solubility in an organic solvent, stability of viscosity in a state of being dissolved in a solvent, and difficulty in causing problems such as gelation and sedimentation.

In the polyarylate (C), the alkali metal used in the interfacial polymerization during the production, the alkaline earth metal contained therein, and the alkali metal or alkaline earth metal mixed in the raw materials are mixed as impurities. come. Further, when washing is performed using an alkaline aqueous solution to remove the residual monomer, an alkali metal or an alkaline earth metal is mixed. The free halogens include, for example, unreacted carboxylic acid chlorides, alkali metal or alkaline earth metal halides as by-products, hydrochloric acid, phase transfer catalysts, and those derived from surfactants.

In order to obtain a polyarylate used as a low dielectric electronic material having an excellent low dielectric loss tangent, the total content of alkali metals, alkaline earth metals and free halogens in the polyarylate must be suppressed to 250 ppm or less. Is required, preferably 150 ppm or less, more preferably 50 ppm or less, and most preferably 20 ppm or less.
It is as follows. The low dielectric loss tangent is the most important characteristic in that when polyarylate is used as an electronic material, transmission loss can be reduced. The lower this value is, the lower the loss becomes, the more preferable the electronic material is.

More specifically, the content of alkali metal and alkaline earth metal is more preferably 100 ppm or less.
It is more preferably at most 30 ppm, most preferably at most 10 ppm. The content of free halogen in the polyarylate (C) is preferably 100 ppm or less, more preferably 30 ppm.
The following is more preferable, and 10 ppm or less is most preferable.
Reduction of these metals and free halogens is also important in obtaining a stable low dielectric loss tangent that can withstand abuse in a high temperature and high humidity environment.

In order to obtain a further excellent low dielectric electronic material, the content of the phenolic hydroxyl group derived from the raw material monomer in the polyarylate (C) is preferably suppressed to 200 ppm or less, more preferably 100 ppm or less. It is more preferably at most 30 ppm, most preferably at most 10 ppm.

By reducing these impurities, it is possible to provide an electronic material having a low dielectric loss tangent and a high reliability under a high temperature and high humidity environment. The reliability under a high-temperature and high-humidity environment is preferably such that the change in the dielectric loss tangent when stored at 60 ° C. and 95% RH (relative humidity) for 1000 hours is less than 35%, and less than 20%. It is more preferred that there be.

By using these two conditions, that is, a polyarylate having the specific structure described above and having a total content of alkali metals, alkaline earth metals and free halogens of 250 ppm or less, The dielectric loss tangent at 1 GHz is 2.0 × 1
0 ^-3 can be obtained a low-dielectric electronic material or less. That is, the low dielectric property in the present invention means that the dielectric loss tangent at 1 GHz is 2.0 × 10 ⁻³ or less, and it is particularly preferable that the dielectric constant at 1 GHz is 2.9 or less.

Next, the polyarylate (C) used in the present invention
The production method will be described in detail. As a method for synthesizing polyarylate, an interfacial polymerization method, a solution polymerization method, and the like are known, but as a method for producing polyarylate (C) used in the present invention, the obtained polyarylate has high purity and low dielectric loss tangent. Since the product can be obtained in a short time, the interfacial polymerization method is preferable.

First, a halide of one or more dicarboxylic acids selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid, wherein the proportion of terephthalic acid in the dicarboxylic acid is 40 mol% or less ( A ′) Organic Solvent Solution and General Formula (IV)

[0059]

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(Wherein Q and R each have 1 to 1 carbon atoms)
An alkyl group of 4, m and n each represent an integer of 0 to 4) and a general formula (V)

[0061]

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Dihydric phenol compound (B ')
And a polyhydric acid is obtained by interfacial polycondensation of the dicarboxylic acid halide (A ′) and the dihydric phenol compound (B ′).

As a more specific production method, the above-mentioned dicarboxylic acid halide (A ′) is dissolved in an organic solvent such as toluene or methylene chloride, and the above-mentioned dihydric phenol (B ′) is dissolved in an aqueous alkali metal solution. Are dissolved in the range of 0.1 to 2 mol / L, and the two solutions are brought into contact with each other to interfacially polymerize a dicarboxylic acid halide and a dihydric phenol to obtain a polyarylate.

At this time, it is preferable to add a phase transfer catalyst to the organic solvent since the reaction is accelerated. Examples of such a phase transfer catalyst include ammonium salts such as methyltrioctylammonium chloride and benzyltriethylammonium chloride;
And phosphonium salts such as tetrabutylphosphonium bromide.

It is preferable to remove the oxygen of the water to be used since the coloring of the resulting polyarylate can be suppressed. It is also possible to add a surfactant. The polycondensation reaction may be a batch type or a continuous type. The reaction temperature is between -5 and
A temperature of 100 ° C. and a temperature not exceeding the boiling point of the solvent may be mentioned, but a temperature of 0 to 80 ° C. is preferred.

According to the present invention, a polyarylate obtained by interfacial polycondensation of a dicarboxylic acid halide and a dihydric phenol compound as described above is used as a reaction solvent or an organic solvent solution obtained by dissolving it in another organic solvent. The polyarylate is precipitated as a fine precipitate by contacting it with a poor solvent of the arylate, and the polyarylate precipitate is then washed with one or more of water and a hydrophilic solvent.

That is, (a) a precipitation and purification operation in which the resulting polyarylate in an organic solvent is brought into contact with a poor solvent for polyarylate to obtain polyarylate as fine precipitates;
And (b) by combining the obtained fine precipitate of polyarylate with a washing and purifying operation of washing with water or at least one hydrophilic solvent, whereby the total content of alkali metals, alkaline earth metals and free halogens is reduced. 250
ppm or less, the dielectric loss tangent at 1 GHz is 2.0 × 1
0 ^-3 or less polyarylate (C) is obtained.

The precipitation purification operation (a) is a method in which a poor solvent is brought into contact with an organic solvent solution in which polyarylate is dissolved to precipitate polyarylate as fine precipitates. Chloroform, methylene chloride, tetrachloroethane, chlorobenzene, tetrahydrofuran, 1,3-dioxolan, N-
Examples include methylpyrrolidinone or anisole.

The poor solvent for polyarylate is not particularly limited as long as it is soluble in an organic solvent solution in which polyarylate is dissolved and does not dissolve polyarylate. For example, alcohols such as methanol, acetone and 2- And ketones such as butanone.

In particular, in order to increase the purification efficiency, it is necessary to continuously introduce the organic solvent solution in which the polyarylate is dissolved and the poor solvent of the polyarylate into a high-shear type mixing machine, and to continuously perform a precipitation operation. preferable. It is also effective to use a batch type, a high-rotation speed blade that revolves on its own axis, or a sedimentation purification operation using a mixing machine that performs stirring with a plurality of blades including a high-speed blade. In any case, if the peripheral speed of the stirring blade is 10 to 30 m / sec, the purification efficiency is high. If the peripheral speed is less than the above range, the precipitation becomes coarse and the purification efficiency is not sufficient, and if the rotation speed is higher than this range, the problem of excessive heat generation due to shearing tends to occur.

Obtaining a fine precipitate of polyarylate in this purification step makes removal of impurities from polyarylate more efficient. Specific examples of the fine precipitate include a precipitate formed as a polyarylate powder having a particle diameter of 100 μm or less.

In the above-mentioned precipitation operation, a solution of an organic solvent in which polyarylate is dissolved is used. In order to easily perform this operation, the organic solution phase obtained by performing the polyarylate synthesis step is directly used as a poor solvent. It is good to contact. In this case, the organic solvent used for polyarylate synthesis is preferably a solvent having high solubility of polyarylate such as methylene chloride. At this time, if the solubility of the polyarylate in the organic solvent is insufficient, the purification by the precipitation operation is not sufficiently performed, and the removal of the residual phenolic hydroxyl group derived from the phenol monomer may be insufficient.

In the (b) washing and purifying operation of polyarylate, the fine precipitate of polyarylate obtained by the above-mentioned sedimentation operation is washed with at least one of ion-exchanged water and a hydrophilic solvent. The temperature of the cleaning liquid at this time is preferably 50 ° C. or higher, and more preferably 75 ° C. or higher. Further, the hydrophilic solvent is preferably an alcohol. In order to effectively reduce the contents of alkali metals, alkaline earth metals and free halogens, it is preferable that the washing operation is repeated at least twice.

As for the purification and purification of polyarylate, it is possible to wash the organic solvent solution of polyarylate with water or alkaline water before the above-mentioned precipitation and purification of polyarylate. The method of washing the precipitate with ion-exchanged water or a hydrophilic solvent,
It is more effective in effectively reducing the content of alkali metals, alkaline earth metals and free halogens.Washing an organic solvent solution of polyarylate with water or alkaline water can reduce fine polyarylate precipitation. Must be performed in combination with cleaning.

The total content of alkali metal, alkaline earth metal and free halogen remaining in the polyarylate by these purification operations is 250 ppm or less, preferably 100 ppm or less, more preferably 30 ppm or less.
pm or less, more preferably 10 ppm or less, and the dielectric loss tangent at 1 GHz is 2.0 × 1
0 ^-3 or less is polyarylate (C) can be produced.

The polyarylate (C) of the present invention has a total content of alkali metal, alkaline earth metal and free halogen of 250 ppm or less and a dielectric loss tangent at 1 GHz of 2.0 × 10 ⁻³ or less. The polyarylate (C) of the present invention has a glass transition temperature (Tg) of 260.
It exhibits high heat resistance shown at ℃ 310 ° C., its tensile strength is generally 100-240 MPa, and in a preferred example, it is 140-240 MPa, and its tensile elastic modulus is generally 1.5-3.0 GPa. In a preferred example, it is 2.5 to 3.0 GPa, and its elongation at break is generally 30 to 120%, and in a preferred example, it is 70 to 120 GPa.
~ 120%.

Therefore, the low dielectric electronic material comprising the polyarylate (C) of the present invention has excellent mechanical properties, high heat resistance and low dielectric loss tangent, and is used in the form of, for example, a sheet or a laminate. be able to. In the present invention, "sheet" means a sheet or film having a continuous structure formed into a planographic shape, and its thickness is not particularly limited, but is usually 1 to 500 µm.

Next, a low dielectric electronic material obtained from a cured product of a resin composition for electronic materials containing a polyarylate (C) and a thermosetting resin (D) will be described. That is,
This low-dielectric electronic material comprises a cured product of a resin composition for electronic materials containing a polyarylate (C) and a thermosetting resin (D), and contains an alkali metal, an alkaline earth metal, and a free halogen in the composition. Is less than 200 ppm, the dielectric loss tangent at 1 GHz after the thermosetting resin component is cured is 3.0 × 10 ⁻³ or less, and the low dielectric element has excellent adhesiveness to a metal film or the like. Material.

The content of residual phenolic hydroxyl groups contained in the low dielectric electronic material formed from the composition containing the polyarylate (C) of the present invention and the thermosetting resin (D) is 200 ppm or less. It is preferable from the viewpoint of obtaining a resin composition for electronic materials having a low dielectric loss tangent and a low dielectric constant.
The low dielectric electronic material formed from the composition containing the polyarylate (C) and the thermosetting resin (D) of the present invention preferably has a dielectric constant at 1 GHz of 3.0 or less.

The above-mentioned polyarylate (C) is excellent in compatibility with the thermosetting resin (D), and is characterized in that its compounding is easy. The resin composition for electronic materials containing the polyarylate (C) and the thermosetting resin (D) of the present invention has high mechanical properties (for example, a tensile strength of 60 to 100 MPa) and high adhesiveness (for example, a metal foil). Has an adhesive strength of 1.9
(2.3 N / m), and exhibits excellent chemical resistance and excellent fluidity during hot press molding.

As chemical resistance, it has resistance to acids and bases. For example, a 10% sodium hydroxide solution at 40 ° C. or 4%
No abnormality is shown when immersed in a 30% hydrochloric acid solution at 0 ° C., and the weight change is 0.4% by weight or less. Further, it has a feature that the solvent resistance to the solvent species that dissolves the polyarylate described above is enhanced. As for the fluidity at the time of hot press molding, the filling property of the composition into the circuit is good even when laminated on a wiring board, and the hot press molding at a temperature of 250 ° C or less is difficult with polyarylate alone. Becomes easier.

Examples of the thermosetting resin (D) used include epoxy resin, diallyl phthalate resin, bismaleimide-triazine resin, vinylbenzyl ether resin, isocyanurate resin, benzodiclobutene resin, divinylbenzene resin and polybutadiene. Examples include one or more thermosetting resins selected from the group consisting of base resins. Among them, epoxy resins are preferable, and active ester-curable epoxy resins are particularly preferable.

The epoxy resin used in the present invention comprises a main component and a curing agent. The main components of the epoxy resin include cresol novolak type epoxy resin, phenol novolak type epoxy resin, naphthol-modified novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, and biphenyl type epoxy resin. resin,
Phenolic glycidyl ether type epoxy resin such as triphenyl type epoxy resin and tetraphenyl type epoxy resin,

Alcohol-based glycidyl ether type epoxy resins such as polypropylene glycol and hydrogenated bisphenol-A, dicyclopentadiene type epoxy resins containing a dicyclopentadiene skeleton, naphthalene type epoxy resins containing a naphthalene skeleton, hexahydrophthalic anhydride And glycidylamine-type epoxy resins using polyamines such as diaminodiphenylmethane as raw materials, alicyclic epoxy resins, and mixtures thereof.

Among these epoxy resins, in order to obtain good heat resistance and low dielectric loss tangent, cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl type (alkylbiphenol type) epoxy resin, dicyclopentadiene type One or more epoxy resins selected from the group consisting of epoxy resins are particularly preferred.

As a curing agent for the epoxy resin, an active ester is preferable from the viewpoint of providing a low dielectric loss tangent. Examples of the active ester include an aliphatic or aromatic ester having two or more ester groups in a molecule. These active esters are compounds in which the phenolic hydroxyl group of an aromatic compound such as polyfunctional phenol or naphthol is esterified with an aromatic acid or an aliphatic acid, and the ester group reacts with the epoxy group of the epoxy resin. In addition, it has an effect of suppressing the generation of a highly polar hydroxyl group during the ring opening reaction of the epoxy group.

From the viewpoint of providing excellent heat resistance and a low dielectric loss tangent, aromatic esters are particularly preferable. Among them, the following general formula (III):

[0088]

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(Wherein R ¹ is

Embedded image Wherein S, T, U, V and W are each an alkyl group having 1 to 4 carbon atoms, and o and t are each 0
P is an integer of 0 to 3, q and r are each 0
R ² represents an integer of

Embedded image

Wherein k represents 2 to 4
And an aromatic ester represented by the following formula:
Among them, divalent esters obtained from α-naphthol and isophthalic acid have excellent solubility in a solvent that dissolves the above-mentioned polyarylate (C) and provide a cured product having a low dielectric loss tangent. That is, di (α-naphthyl) isophthalate is particularly preferred.

These aromatic esters can be prepared from a polycarboxylic acid or a polycarboxylic acid halide having an R ² portion and a monohydric phenol having an R ¹ portion by a known and ordinary Schotten-Baumann method, It can be synthesized by an acetic acid method or a direct synthesis method. When synthesizing these aromatic esters, a dihydric phenol such as alkyl biphenol, bisphenol A, resorcin and the like may coexist to form an aromatic ester having a long chain.

The resin composition for electronic materials containing the polyarylate (C) and the thermosetting resin (D) of the present invention may contain an imidazole compound, an organic phosphine compound,
A curing accelerator such as an organic phosphite compound, a phosphonium salt, an amine compound, a quaternary ammonium salt, or a urea compound is used. In addition, the resin composition for electronic materials of the present invention has a polyarylate (C) and a thermosetting resin (D) for the purpose of adjusting the solution viscosity to an appropriate value when coating or impregnating the resin composition for electronic materials. ) And an organic solvent that dissolves the curing agent.

The method for obtaining the resin composition for electronic materials containing the polyarylate (C) and the thermosetting resin (D) of the present invention is not particularly limited. For example, the polyarylate (C) and the thermosetting resin (D) may be used. D) and chloroform, methylene chloride,
An example is a method of dissolving in a solvent selected from the group consisting of tetrachloroethane, chlorobenzene, tetrahydrofuran, 1,3-dioxolane, N-methyl-2-pyrrolidinone, and anisole, and then evaporating the used solvent at a temperature of 10 to 200 ° C. it can. Then, if necessary, 100-30
A heat treatment is performed at a temperature of 0 ° C. for about 0.1 to 3 hours, and the thermosetting resin (D) is thermoset to obtain a low dielectric electronic material comprising the above resin composition for electronic materials. be able to.

During this time, the reaction between the ester of the polyarylate (C) and the thermosetting resin (D) may be performed. Further, in the composition of the present invention, it is preferable that the thermosetting resin also has high purity, and the total content of alkali metals, alkaline earth metals and free halogens is 250 ppm or less.

When the weight ratio of the thermosetting resin (D) / polyarylate (C) in the composition is 4/96 or more, more excellent adhesion and resistance than the case of the polyarylate (C) alone. It can impart chemical properties and excellent fluidity during hot press molding.

Further, when a resin composition for an electronic material containing a polyarylate (C) and a thermosetting resin (D) is dissolved in an organic solvent, and a substrate is coated as a varnish or a cloth or a nonwoven fabric is impregnated. When 96 parts by weight of the thermosetting resin (D) is mixed with 4 parts by weight or more of the polyarylate (C), a suitable varnish thickening effect by the polyarylate (C) becomes clear. That is, when 4 parts by weight or more of the polyarylate (C) is blended with 96 parts by weight of the thermosetting resin (D), the viscosity of the varnish becomes 500 to 3000 centipoise, and the shape retention in the coating and drying step is improved. It is possible to obtain a viscosity suitable for processability in the impregnation operation and for preventing sedimentation of the filler when a high specific gravity inorganic filler such as silica is mixed.

The cured product of the resin composition for electronic materials containing the polyarylate (C) of the present invention and the thermosetting resin (D) is as follows:
Because of its excellent mechanical properties, high heat resistance, and low dielectric loss tangent, it can be used in the form of sheets and laminates, etc., and prepregs based on adhesive sheets, build-up coating materials, cloth or nonwoven fabric It is suitably used as a low dielectric electronic material provided in the form of a sheet with a metal foil such as a copper foil with a resin or a metal foil-clad laminate for a flexible wiring board, for example, a printed wiring board or a semiconductor encapsulant.

The low dielectric electronic material comprising a cured product of the resin composition for an electronic material of the polyarylate (C) and the thermosetting resin (D) of the present invention and a sheet comprising the same are made of an alkali metal and an alkaline earth metal. And the total content of free halogens is 250 ppm or less, and the dielectric loss tangent at 1 GHz is 3.0 × 10 ⁻³ or less.

Further, a low dielectric electronic material comprising a cured product of the resin composition for an electronic material of the polyarylate (C) and the thermosetting resin (D) of the present invention, and a sheet comprising the same,
Although the dielectric properties are slightly lower than those of polyarylate alone, the adhesiveness, chemical resistance and fluidity during molding are excellent as described above, and the glass transition temperature (Tg) of the thermosetting resin (D ), But generally 120-300 ° C
And a preferred example shows high heat resistance at 160 to 300 ° C.

Further, the low dielectric electronic material sheet made of a cured product of the resin composition for electronic materials of the polyarylate (C) of the present invention and the thermosetting resin (D) is immersed in water at 23 ° C. for 24 hours. The water absorption test also shows a low water absorption, and the water absorption is only 0.1 to 0.7% by weight. Low water absorption is important not only for insulation reliability but also for suppressing the adverse effect of enhancing dielectric properties.

Here, the method for producing the sheet of the present invention will be described. When a sheet is produced using the low dielectric electronic material comprising the polyarylate (C) of the present invention, the polyarylate (C) is dissolved in an organic solvent to form a solution. By evaporating and removing the solvent by the solvent casting method described above, the sheet can be processed.

As the organic solvent used, chloroform,
Methylene chloride, tetrachloroethane, chlorobenzene,
Tetrahydrofuran, 1,3-dioxolan, dimethylacetamide, N-methylpyrrolidinone, anisole,
Examples thereof include cyclohexanone, toluene, and xylene, and two or more of these may be used in combination.

When a sheet is manufactured using the resin composition for an electronic material comprising the polyarylate (C) of the present invention and the thermosetting resin (D), for example, first, the thermosetting resin (D) is used. Is dissolved in an organic solvent, the polyarylate (C) is dissolved in the organic solvent solution, and then the solution is cast. The organic solvent is volatilized and removed by a known conventional solvent casting method and the like. By doing so, it can be manufactured as a sheet. The order of dissolution of both may be changed.

When the thermosetting resin (D) contained in the resin composition for an electronic material is completed, the fluidity of the resin composition for an electronic material is reduced. It is important to use a sheet made of semi-cured material because it is damaged. The condition of the semi-curing of the resin composition for electronic materials is not particularly limited as long as the semi-cured product of the resin composition for electronic materials to be used can be shaped, and is not particularly limited.
And a semi-cured product is obtained by heating for 4 to 30 minutes.

Next, a laminate obtained by laminating the sheets of the present invention will be described. The sheet of the present invention may be used alone, or a plurality of sheets may be laminated, heated and pressed, and used as a laminate having a desired thickness. Further, the sheet of the present invention and a printed wiring board or the like can be formed by lamination and adhered, which is also useful for manufacturing a multilayer wiring board for high-frequency communication.

Further, a metal foil such as gold, copper, aluminum or the like may be laminated and formed on both sides or one side of the sheet of the present invention to easily form a sheet with a metal foil in which both sides or one side are covered with a metal foil. As a method for producing a sheet with a metal foil, a method in which the sheet and the metal foil are heated and pressed (applicable to a sheet having a metal foil on both sides or one side), and a method in which the above solvent casting method is performed on the metal foil (Applicable to metal foil on one side).

In particular, to obtain a sheet with a single-sided metal foil suitable for forming a laminate of a resin composition for an electronic material comprising a polyarylate (C) and a thermosetting resin (D), The solvent casting method described above is advantageous in that an appropriate semi-cured state is easily obtained. The sheet with a metal foil of the present invention may be formed by laminating the above-mentioned sheet or a printed wiring board after etching a copper foil as necessary to form a circuit, and for manufacturing a multilayer wiring board for high frequency communication. Is also useful.

In the method of laminating the sheet and the sheet with metal according to the present invention, two or more sheets are sandwiched between platens, for example, at 250 to 350 ° C., preferably 280 to 350 ° C.
A method of performing pressure bonding at a temperature of 350 ° C. is exemplified. In particular, when a semi-cured sheet of the resin composition for an electronic material of the polyarylate (C) and the thermosetting resin (D) is used, the temperature can be reduced to about 150 to 240 ° C. However, in this case, a heating time for curing the thermosetting resin is required. The pressure at this time is not particularly limited, but is preferably in the range of 1 to 40 MPa. It is preferable to perform the treatment in a vacuum in many cases because the rate of void generation can be reduced.

The sheet of the present invention is preferably applied as a single-sided, double-sided or multi-layer printed wiring board in a form containing a cloth such as glass, aramid, polyester or the like, and a filler such as silica or mica, if necessary. Sheets with metal foil, adhesive sheets, build-up coating materials, such as prepregs containing base materials and non-woven fabric base materials, resin-coated copper foil as a build-up material for multilayer wiring boards and metal foil-clad laminates for flexible wiring boards It is particularly useful for high frequency applications such as 500 MHz or higher, preferably 1.0 to 20 GHz band utilizing low dielectric loss tangent.

[0110]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the scope of the present invention is not limited to these Examples. The measurement and evaluation methods used will be described first.

<Measurement of Glass Transition Temperature (Tg)> The tan δ peak temperature in a dynamic solid viscoelasticity test at 1 Hz and 5 ° C./min with Seiko DMS200 was defined as Tg.

<Measurement of Dielectric Characteristics> A 1M frequency was measured using a dielectric characteristic evaluation device (Q meter QM-102D manufactured by Yokogawa Electric Corporation).
The dielectric loss tangent and dielectric constant in Hz were determined at 23 ° C.
Separately, the dielectric loss tangent and the dielectric constant at a frequency of 1 GHz were determined at 23 ° C. using a dielectric property evaluator 4291B manufactured by Agilent Technologies.

The sample used for the dielectric property evaluation was 60
After storing at 1000 ° C. and 95% RH (relative humidity) for 1000 hours, the above measurement at the frequency of 1 GHz is performed again, and the dielectric loss tangent increase rate (%) = [(dielectric tangent after storage−dielectric tangent before storage) / Dielectric tangent before storage] × 100.

<Evaluation of Solder Heat Resistance> After the sample was immersed in a 300 ° C. molten solder bath for 30 seconds, changes in appearance such as swelling, peeling, and surface roughness were examined.

<Measurement of Tensile Characteristics> A sample was measured using a universal testing machine (Shimadzu Corporation, Autograph AG-2000).
A tensile test was performed at a crosshead speed of 1 mm / min to determine the tensile strength. <Measurement of Adhesion to Copper Foil> Using a universal testing machine (Shimadzu Autograph AG-2000), crosshead speed =
The copper foil was vertically peeled at 5 cm / min to determine the peel strength.

<Quantitative Determination of Impurities> (Quantification of Alkali Metals and Alkaline Earth Metals) First, a sample powder was subjected to fluorescent X-ray analysis using ZSX100e manufactured by Rigaku Denki, and alkali metal and alkaline earth metal contained in the sample were analyzed. As a result, it was preliminary confirmed that 99% or more was Na. Subsequently, high-precision quantification of Na was performed with an inductively coupled plasma emission analyzer. In the plasma emission analysis operation, first, a sample was irradiated with microwaves in a mixed aqueous solution of sulfuric acid and nitric acid to decompose the sample, and the solution for measurement was applied to an ICP apparatus (Perkin Elmer OPTIMA 3300DV) to perform luminescence analysis and quantitate. The results are shown in the table as Na (ppm)
Indicated by

(Quantitative Determination of Free Halogen) First, it was confirmed by the above-mentioned X-ray fluorescence analysis that 99% or more of the free halogen contained in the sample was chlorine. Next, the Mitsubishi Chemical TO
Using X-10 °, the sample was burned in a stream of argon / oxygen to introduce hydrogen chloride into a titration cell, and then the amount of free chlorine was determined by automatic titration using silver ions. C in the table
1 (ppm).

(Quantitative Determination of Residual Phenolic Hydroxyl Group) A sample was dispersed in acetonitrile, N, O-bis (trimethylsilyl) trifluoroacetamide was added, and the mixture was irradiated with ultrasonic waves for 5 minutes to remove residual dihydric phenol derived from the raw material. Extraction in a silylated form is performed by gas chromatography (GC-
14B, OV-1 column).
It was shown by weight% of H group.

Example 1 1.031 kg of isoterephthaloyl chloride, 0.258 kg of terephthaloyl chloride,
A solution consisting of 0.057 kg of methyltrioctylammonium chloride, and 27.3 kg of toluene;
A solution consisting of 1.540 kg of 3,3′-5,5′-tetramethylbiphenol, 0.648 kg of sodium hydroxide, and 19.2 kg of deoxygenated water was stirred in a 100 L kettle at 11 ° C. for 30 minutes. Mix and contact.

After the resulting solution was separated by standing, the aqueous phase was removed, and then the toluene phase was washed three times with water. Subsequently, methanol, which is a poor solvent, was added to the obtained toluene phase for 10 minutes each.
L / min, 100 L / min at a feed rate of a continuous type shearing machine (Taipei Kiko Fine Flow Mill FM-25, blade peripheral speed = 15 m / sec) to continuously perform a settling operation (precipitation of polyarylate). went. Next, the obtained polyarylate was collected on a filter medium, and then heated in a kettle at 80 ° C. for 30 minutes.
Washing and filtration were repeated three times for one minute and then dried to obtain a polyarylate powder.

The powder of polyarylate in chloroform (0.1 g / dL) at 30 ° C. had an inherent viscosity determined by an Ubbelohde viscometer of 1.5 dL / g.
Next, a transparent solution obtained by dissolving 5 g of the obtained polyarylate in 95 g of anisole at room temperature was cast on a glass plate, and placed under an air stream of 90 ° C. to volatilize the anisole, thereby forming a transparent film having a thickness of 60 μm. To obtain a polyarylate sheet without voids. Table 1 shows the tensile strength test results of this sheet. The tensile modulus was 2 GPa and the elongation at break was 70%, which was excellent.

11 sheets obtained were laminated, and 310
It was heated and pressed at 2 ° C. and 8 MPa for 2 minutes to obtain a laminate having a thickness of about 600 μm. Table 1 shows the results of the evaluation of the dielectric properties.
Separately, six sheets of the above polyarylate and one piece of copper foil (18 μm thick by Furukawa Circuit Technology) are laminated so that the copper foil (the glossy side is on the front side and the roughened side is on the inside) is the surface layer, and the temperature is 300 ° C. It was heated and pressed at 5 MPa for 1 minute to obtain a copper-clad laminate having a thickness of about 550 μm. Table 1 shows the copper foil peel strength and solder heat resistance.

Example 2 1.031 kg of isoterephthaloyl chloride, 0.258 kg of terephthaloyl chloride,
A solution consisting of 0.057 kg of methyltrioctylammonium chloride and 27.3 kg of methylene chloride, 1.540 kg of 3,3'-5,5'-tetramethylbiphenol, 0.648 kg of sodium hydroxide, and 19 100 L of solution consisting of 2 kg of deoxygenated water
The mixture was stirred and mixed in a kettle at 25 ° C. for 30 minutes and brought into contact.
After standing and separating the resulting solution, the aqueous phase was removed and the remaining methylene chloride phase was replaced with a 10 kg sodium carbonate solution (0.25 mol /
Washing by stirring and mixing with L) was repeated three times.

The obtained methylene chloride phase was subjected to a sedimentation operation (polyarylate precipitation) in a two-shaft mixer (BDM mixer manufactured by Inoue Seisakusho, peripheral speed of high-speed blade = 20 m / sec) containing 200 kg of acetone. The collected polyarylate was collected on a filter medium, and then washed and filtered three times with hot water at 80 ° C. for 30 minutes each in a kettle, and thereafter,
After drying, a powder of polyarylate was obtained. The powder of this polyarylate is put in chloroform (0.1 g / dL) at 30 ° C.
The inherent viscosity determined by an Ubbelohde viscometer was 2.1 dL / g.

5 g of the polyarylate thus obtained was added to 9
A transparent solution obtained by dissolving in 5 g of tetrahydrofuran at room temperature was cast on a glass plate, and placed under an air stream at 40 ° C. to evaporate the tetrahydrofuran to obtain a 60 μm-thick transparent and void-free polyarylate sheet. . Table 1 shows the tensile strength test results of this sheet. The tensile modulus was excellent at 1.4 GPa and the elongation at break was excellent at 30%. The results of the same operation and evaluation as in Example 1 are shown in Table 1 below.

Example 3 1.031 kg of isoterephthaloyl chloride, 0.258 kg of terephthaloyl chloride,
A solution consisting of 0.057 kg of methyltrioctylammonium chloride and 27.3 kg of methylene chloride, 1.540 kg of 3,3'-5,5'-tetramethylbiphenol, 0.648 kg of sodium hydroxide and 19 A solution consisting of 0.2 kg of deoxygenated water was stirred and mixed in a 100 L kettle at 25 ° C. for 30 minutes and brought into contact. After standing and separating the resulting solution, the aqueous phase was removed and the remaining methylene chloride phase was replaced with a 10 kg sodium carbonate solution (0.25 mol /
Washing by stirring and mixing with L) was repeated three times.

The obtained methylene chloride phase was subjected to a precipitation operation (polyarylate precipitation) in a two-shaft mixer (BDM mixer manufactured by Inoue Seisakusho, peripheral speed of high-speed blade = 13 m / sec) containing 100 kg of acetone. The resulting polyarylate was collected on a filter medium, and further washed and filtered once with warm water at 50 ° C. for 30 minutes in a kettle. Then, it dried and obtained the powder of polyarylate. The inherent viscosity of this polyarylate powder measured with an Ubbelohde viscometer at 30 ° C. in chloroform (0.1 g / dL) is as follows:
It was 2.1 dL / g.

A transparent solution obtained by dissolving 5 g of the obtained polyarylate in 95 g of tetrahydrofuran at room temperature was cast on a glass plate, and placed under an air stream at 40 ° C. to volatilize the tetrahydrofuran and evaporate the tetrahydrofuran to a thickness of 60 μm. A void-free polyarylate sheet was obtained. The results of the same operation and evaluation as in Example 1 are shown in Table 1 below.

Example 4 1.031 kg of isoterephthaloyl chloride, 0.258 kg of terephthaloyl chloride,
0.017 kg benzoyl chloride, 0.057 kg methyltrioctylammonium chloride, and 27.3 k
g of methylene chloride and 0.770 kg of 3,3'-5,5'-tetramethylbiphenol, 1.1
A solution consisting of 14 kg of 9,9-bis (4-hydroxyphenyl) fluorene, 0.648 kg of sodium hydroxide, and 19.2 kg of deoxygenated water was stirred and mixed in a 100 L kettle at 11 ° C. for 30 minutes and contacted. I let it.

After the resulting mixed solution was separated by standing, the aqueous phase was removed, and then the washing was repeated three times with stirring and mixing the methylene chloride phase with 10 kg of water to bring them into contact with each other. The obtained methylene chloride phase was mixed with 200 kg of acetone using a twin-screw mixer (BDM mixer manufactured by Inoue Seisakusho, peripheral speed of high-speed blade =
(20 m / sec) to perform a precipitation operation (polyarylate precipitation). Next, the obtained polyarylate was collected on a filter medium, and then washed with warm water at 70 ° C. for 30 minutes in a kettle.
This was repeated twice and then dried to obtain a polyarylate powder. The inherent viscosity of this polyarylate powder measured with a Ubbelohde viscometer at 30 ° C. in chloroform (0.1 g / dL) was 1.5 dL / g.

5 g of the polyarylate thus obtained was added to 9
A transparent solution obtained by dissolving in 5 g of anisole at room temperature was cast on a glass plate and placed under an air flow of 100 ° C. to volatilize the anisole to obtain a 60 μm thick transparent and void-free polyarylate sheet. Was. Table 1 below shows the results of the same evaluation as in Example 1.

Comparative Example 1 1.031 kg of isoterephthaloyl chloride, 0.258 kg of terephthaloyl chloride,
A solution consisting of 0.057 kg of methyltrioctylammonium chloride, and 27.3 kg of toluene;
A solution consisting of 1.540 kg of 3,3′-5,5′-tetramethylbiphenol, 0.648 kg of sodium hydroxide, and 19.2 kg of deoxygenated water was stirred in a 100 L kettle at 11 ° C. for 30 minutes. Mix and contact.

After the resulting solution was separated by standing, the aqueous phase was removed, and then the toluene phase was washed three times with water. Subsequently, the pressure inside the kettle was reduced to remove toluene and water, and the obtained polyarylate (inherent viscosity = 1.6 dL / g) was washed with warm water at 40 ° C. for 30 minutes in the kettle and filtered once. afterwards,
The powder was dried to obtain a polyarylate powder.
The same operation as described above was performed. The same operation and evaluation as in Example 1 were performed on the obtained sheet, and the results are shown in Table 1.

(Comparative Example 2) In Example 3, 1.54
The same operation as in Example 2 was carried out except that an equimolar amount of bisphenol A was used in place of 0 kg of 3,3′-5,5′-tetramethylbiphenol to obtain a polyarylate powder (inherent viscosity = 1. 7 dL / g). After that, the same operation and evaluation as in Example 1 were performed, and the results are shown in Table 1.

(Comparative Example 3) In Example 3, 1.54
The same operation as in Example 2 was performed, except that an equimolar amount of 3,3′-5,5′-tetramethylbisphenol F was used instead of 0 kg of 3,3′-5,5′-tetramethylbiphenol, Polyarylate powder (inherent viscosity = 1.6
dL / g). Thereafter, the same operation as in Example 1 was performed, and the evaluation results are shown in Table 1.

(Comparative Example 4) In Example 3, 1.54
Example 1 except that 0 kg of 3,3′-5,5′-tetramethylbiphenol was replaced with an equimolar amount of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (manufactured by Nippon Steel Chemical). By performing the same operation as in Example 3, a powder of polyarylate (inherent viscosity = 1.3 dL / g) was obtained.
Next, a transparent solution obtained by dissolving 5 g of the obtained polyarylate in 95 g of methylene chloride at room temperature was cast on a glass plate, and placed under an air stream at 40 ° C. to evaporate tetrahydrofuran to evaporate the transparent void having a thickness of 60 μm. To obtain a sheet of polyarylate free of polystyrene. The results of the same operation and evaluation as in Example 1 are shown in Table 1 below.

Comparative Example 5 1.031 kg of isoterephthaloyl chloride, 0.258 kg of terephthaloyl chloride,
And 1.540 kg of 3,3′-5,5′-tetramethylbiphenol with 26.3 kg of pyridine and 265 kg
With a solvent consisting of 1,1,2,2-tetrachloroethane in a 300 L kettle at 60 ° C. for 4 hours and further at 10 ° C.
For 2 hours. The resulting liquid was gradually added to 730 kg of methanol to obtain a precipitate. The resulting precipitate is filtered off, and 200 kg of methanol and further 200 k
After washing with g of acetone, it was dried to obtain polyarylate, but its inherent viscosity was 0.3 dL / g, and a tough sheet was not obtained. Table 3 shows the evaluation results.

Comparative Example 6 1.624 kg (8 mol) of isophthaloyl chloride, 0.406 kg (2 mol) of terephthaloyl chloride, 2.423 kg (10 mol) of 3,
3'-5,5'-tetramethylbiphenol, 3.16
A solution of 28 kg of pyridine and 28 kg of chloroform was stirred in a 300 L kettle at 0 ° C. for 8 hours. Thereafter, 42 kg of chloroform was further added, and the resulting solution was poured into methanol. After washing with acetone, polyarylate flakes were obtained. Its inherent viscosity was 1.7 dL / g.

A solution obtained by dissolving 5 g of the obtained polyarylate in 95 g of tetrahydrofuran at room temperature was poured into methanol under high-speed stirring at 10,000 revolutions (peripheral speed = 27 m / sec) in a 1 L Oster blender to obtain a precipitate. . The resulting precipitate was used as a 0.5% by weight aqueous dispersion, suctioned on a filter paper, and then dried to obtain a polyarylate powder.
Hereinafter, the results of performing the same operations and evaluations as in Example 1 are shown in Table 1.
Shown in

Example 5 16.5 g of dicyclopentadiene type epoxy resin (Epiclon HP7200, manufactured by Dainippon Ink and Chemicals, Inc.), 13.4 g of di (1-naphthyl) isophthalate, 0.15 g of 2-ethyl Epoxy resin composition consisting of -4-methylimidazole (Na =
(25 ppm, free chlorine = 1 ppm, residual phenolic hydroxyl group = 2 ppm) and 70 g of the polyarylate powder obtained in Example 1 were mixed with 990 g of tetrahydrofuran to obtain a solution. Next, this solution was cast on a stainless steel plate and distributed in an air stream at 70 ° C. for 15 times to evaporate tetrahydrofuran to obtain a sheet of a semi-cured resin composition of a polyarylate and an epoxy resin.

A total of 10 sheets obtained were laminated, and
Approximately 600
A laminated plate of the polyarylate composition having a thickness of μm was obtained. Table 4 shows the evaluation results of the dielectric properties and the tensile strength. Separately,
Nine sheets of the above sheet-like material and one piece of copper foil (18 μm thick by Furukawa Circuit Technology) were coated with copper foil (the glossy surface was on the front side,
Laminated so that the roughened surface is on the inside) and
It was heated and pressed at 0 MPa for 100 minutes to obtain a copper-clad laminate having a thickness of about 560 μm. In order to exhibit excellent fluidity at the time of heat and pressure molding, the temperature at the time of molding may be lower than that of the polyalate alone of Example 1. Table 4 shows the evaluation results of the copper foil peel strength and the solder heat resistance of the obtained copper-clad laminate. The amount of impurities described in Table 4 indicates the amount of impurities in the composition.

Example 6 44.0 g of dicyclopentadiene-type epoxy resin (Epiclon HP7200H, manufactured by Dainippon Ink and Chemicals, 35.7 g of di (1-naphthyl) isophthalate, 0.40 g of 2-ethyl Epoxy resin composition consisting of -4-methylimidazole (Na =
25 ppm, free chlorine = 1 ppm, residual phenolic hydroxyl group = 2 ppm) and 20 g of the polyarylate powder obtained in Example 1 were mixed with 990 g of tetrahydrofuran to obtain a solution. Next, this solution was cast on a stainless steel plate, distributed under an air flow of 70 ° C. for 15 times, and tetrahydrofuran was volatilized to obtain a sheet of a semi-cured resin composition of a polyarylate and an epoxy resin. Thereafter, the same operation as in Example 5 was performed, and the evaluation results are shown in Table 4.

[0143]

[Table 1]

[0144]

[Table 2]

[0145]

[Table 3]

Comparative Example 7 16.5 g of dicyclopentadiene type epoxy resin (Epiclon HP7200, manufactured by Dainippon Ink and Chemicals, Inc.), 13.4 g of di (1-naphthyl) isophthalate, 0.15 g of 2-ethyl Epoxy resin composition consisting of -4-methylimidazole (Na =
(25 ppm, free chlorine = 1 ppm, residual phenolic hydroxyl groups = 1 ppm) and 70 g of the polyarylate powder obtained in Comparative Example 1 were mixed with 990 g of tetrahydrofuran to obtain a solution. Next, the solution was cast on a stainless steel plate.
Anisole was volatilized by distributing 15 pieces under an air flow of 0 ° C. to obtain a sheet of a semi-cured resin composition of a polyarylate and an epoxy resin. Thereafter, the same operation as in Example 5 was performed, and the evaluation results are shown in Table 4.

(Comparative Example 8) 26.1 g of bisphenol A type epoxy resin (manufactured by Ciba, Araldite AER600)
3) 5.1 g of trimellitic anhydride 0.09 g of 2
-Ethyl-4-methylimidazole epoxy resin composition (Na = 10 ppm, free chlorine = 1 ppm, residual phenolic hydroxyl group = 0 ppm) and 70 g of the polyarylate powder obtained in Example 1 were mixed with tetrahydrofuran 99
0 g to obtain a solution. Next, this solution was cast on a stainless steel plate and placed under an air flow of 70 ° C. for 15 minutes to evaporate tetrahydrofuran to obtain a sheet of a polyarylate composition. Thereafter, the same operation as in Example 5 was performed, and the evaluation results are shown in Table 4.

[0148]

[Table 4]

[0149]

Industrial Applicability The present invention has an extremely low dielectric constant of not more than 2.0 × 10 ^-3 at 1 GHz, and has excellent mechanical properties such as heat resistance and tensile strength. Dielectric electronic material composed of polyarylate having the following properties, and in addition to mechanical properties such as excellent heat resistance and tensile strength of the polyarylate, solvent solubility, easy adjustment of solution viscosity, etc. are required as electronic materials. Low-dielectric electronic material comprising a cured product of the resin composition comprising the polyarylate and the thermosetting resin, the sheet and the laminate comprising the low-dielectric electronic material, and the low-dielectric electronic It is possible to provide a method for producing a low dielectric constant polyarylate used for a material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 3/40 H01B 3/40 Z 3/42 3/42 E H05K 1/03 610 H05K 1/03 610J ( 72) Inventor Yasuhiro Kuwana 972-5, Shiinazaki-cho, Midori-ku, Chiba-shi, Chiba Prefecture (72) Inventor Masao Yamada 5-2-3-1-203, Kimizuka, Ichihara-shi, Chiba Prefecture (72) Inventor Yoshinari Yamato Osakidai, Sakura-shi, Chiba Prefecture 1-27-1-203 (72) Inventor Yusho Usami 284-1-2-306 Ishikawa, Sakura-shi, Chiba F-term (reference) 4F071 AA03 AA36 AA42 AA43 AA48 AA81 AA86 AB17 AF02 AF03 AF14 AF40 AF45 AH12 AH13 BA01 BA02 BB02 BC01 4J002 BC132 BE042 BF052 BH022 CD002 CD012 CD022 CD042 CD052 CD062 CD102 CF161 CM022 FD141 FD150 GF00 GQ00 GQ01 HA05 4J029 AA04 AB01 AB07 AC01 AD01 AD03 AD07 AD10 AE03 AE17 BB10A BB12 BB12B BB10B BB12B CB06A HA01 HA05 HB05 JB063 JB123 JB132 JB143 JB153 JC091 JC631 JD08 JE023 JE153 JE213 KA01 KA04 KB06 KB12 KC02 KE01 KE11 KH04 KH05 LA08 LB05 5G305 AA06 AB10 BA12 BA13 CA15 CA11 CA13

Claims (19)

[Claims] 1. The structural unit (A) comprising a repeating unit (-(A)-(B)-) of the structural units (A) and (B).
Is a residue of a dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid, and the proportion of terephthalic acid residues in the residues of the dicarboxylic acid is 40 mol% or less, and the structural unit ( B) is a compound of the general formula (I) (Wherein Q and R each represent an alkyl group having 1 to 4 carbon atoms, and m and n each represent an integer of 0 to 4) and a compound represented by the following general formula (II): Wherein the total content of alkali metal, alkaline earth metal and free halogen is 250 ppm or less, and the dielectric loss tangent at 1 GHz is 2.0 × 10 ^−3. A low dielectric electronic material comprising the following polyarylate (C). 2. The content of residual phenolic hydroxyl groups is 20.
2. The low dielectric electronic material according to claim 1, wherein the content is 0 ppm or less. 3. The low dielectric electronic material according to claim 1, wherein the dielectric constant at 1 GHz is 2.9 or less. 4. A sheet comprising the low dielectric electronic material according to claim 1. 5. A sheet with a metal foil having a metal foil on one or both sides of the sheet made of the low dielectric electronic material according to claim 1. 6. The structural unit (A) comprising a repeating unit (-(A)-(B)-) of the structural units (A) and (B).
Is a residue of a dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid, and the proportion of terephthalic acid residues in the residues of the dicarboxylic acid is 40 mol% or less, and the structural unit ( B) is a compound of the general formula (I) (Wherein Q and R each represent an alkyl group having 1 to 4 carbon atoms, and m and n each represent an integer of 0 to 4) and a compound represented by the following general formula (II): And a polyarylate (C) comprising at least one dihydric phenol residue, an epoxy resin, a diallyl phthalate resin, a bismaleimide-triazine resin, a vinylbenzyl ether-based resin, an isocyanurate-based resin, A content of an alkali metal, an alkaline earth metal and free halogen of at least one thermosetting resin (D) selected from the group consisting of a diclobutene resin, a divinylbenzene resin and a polybutadiene resin;
A resin composition for an electronic material having a content of 50 ppm or less. 7. The resin composition for an electronic material according to claim 6, wherein the weight ratio of polyarylate (C) / thermosetting resin (D) is 96/4 to 4/96. 8. The thermosetting resin (D) is an epoxy resin, and a curing agent for the epoxy resin is a compound represented by the general formula (III): Wherein k is an integer of 2 to 4, and R ¹ is Wherein S, T, U, V and W are each an alkyl group having 1 to 4 carbon atoms, and o and t are each 0
An integer of 0 to 5, q and r are each an integer of 0 to 4 and p is 0
And R ² represents the following: The resin composition for an electronic material according to claim 6, which further comprises an aromatic ester represented by any of the following: 9. The resin composition for an electronic material according to claim 6, wherein the total content of alkali metals, alkaline earth metals and free halogens is 250 ppm or less. 10. The residual phenolic hydroxyl group content is 2%.
The resin composition for an electronic material according to claim 6, wherein the content is not more than 00 ppm. 11. A dielectric material having a dielectric loss tangent of 3.0 at 1 GHz, comprising a cured product of the resin composition for electronic materials according to claim 6.
× 10 ⁻³ or less low dielectric electronic material. 12. A low dielectric electronic material comprising a cured product of the resin composition for electronic materials according to claim 6, which has a dielectric constant at 1 GHz of 3.0 or less. 13. A sheet comprising a semi-cured product of the resin composition for an electronic material according to claim 6. 14. A sheet with a metal foil having a metal foil on one or both sides of a sheet comprising a semi-cured product of the resin composition for electronic materials according to claim 6. 15. A laminate obtained by curing a sheet made of a semi-cured product of the resin composition for electronic materials according to claim 13. 16. A laminated board obtained by curing a sheet with a metal foil having a metal foil on one or both sides of a sheet made of a semi-cured product of the resin composition for electronic materials according to claim 14. 17. A laminate formed by heating and pressing at least two of the sheet according to claim 4 and the sheet with a metal foil according to claim 5 and 14. 18. A dicarboxylic acid halide (A ′) selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid, wherein the proportion of terephthalic acid is 40 mol% or less of all dicarboxylic acids, and a compound represented by the general formula (IV): ) (Wherein Q and R each represent an alkyl group having 1 to 4 carbon atoms, and m and n each represent an integer of 0 to 4) and a compound represented by the following general formula (V): In contact with an organic solvent solution of polyarylate obtained by interfacial polycondensation with any one or more dihydric phenol compounds (B ') represented by
Obtaining a fine precipitate of the polyarylate, and then washing the fine precipitate of the polyarylate with one or more of water and a hydrophilic solvent, an alkali metal,
The total content of alkaline earth metal and free halogen is 250 ppm or less, and the dielectric loss tangent at 1 GHz is 2.
A method for producing a polyarylate of 0 × 10 ⁻³ or less. 19. The content of residual phenolic hydroxyl groups is 2
19. The method for producing a polyarylate according to claim 18, wherein the amount is 00 ppm or less.