JP2001049110A - Low dielectric resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent electric characteristics (low dielectric property) and heat resistance, especially useful for a high-frequency electronic parts for circuit board, insulating material, etc., by making the composition include a specific fluorine-containing aryl ether ketone polymer. SOLUTION: This composition comprises a fluorine-containing aryl ether ketone polymer of formula I [X is a halogen, a lower alkyl or a lower alkoxy; q is 0-4; n is a polymerization degree; m is 0 or 1; R1 is a group of formula II (X' and q' are as shown for X and q, respectively; p is 0 or 1) ; R2 is a bifunctional aromatic group] (e.g. a polymer of formula III, etc.). The polymer is obtained, for example, by subjecting 2,3,4,5,6-pentafluorobenzoyl chloride and an alkoxybenzene to a Friedel-Crafts reaction in an organic solvent to give p-(2,3,4,5,6-pentafluorobenzoyl)alkoxybenzene, dealkylating p-(2,3,4,5,6- pentafluorobenzoyl)alkoxybenzene to give a compound of formula IV (q is 0 or 1) and heating the compound in the presence of a basic compound in an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a low dielectric resin composition. More specifically, the present invention relates to a low dielectric resin composition having excellent electrical properties (low dielectric properties) and heat resistance, and particularly useful for high-frequency electronic components such as wiring boards and insulating materials. .

[0002]

2. Description of the Related Art Engineering plastics are plastics used for applications such as electronic and electric parts, automobile parts and mechanical parts. Generally, the higher the heat-resistant temperature, the higher the dielectric constant and the dielectric loss tangent. There were no plastics that had both heat resistance and low dielectric properties.

For example, typical examples of heat-resistant engineering plastics include polyimide (PI), polyetherimide (PEI), polyphenylene sulfide (PPS), polyarylate (PAR), liquid crystal polymer (LCP), and polyether sulfone ( PES), polyketone (PK), etc. have excellent heat resistance and mechanical properties and are used for various applications. However, these polymers have a high dielectric constant especially in a high frequency range, and therefore, they are used for high frequency electronic devices. There is a problem that there is a limit to use.
In addition, polyacetal (POM), polyethylene terephthalate (PET), polybutylene terephthalate (P
Engineering plastics such as BT) and polyamide (PA) are inadequate in terms of heat resistance and also have high dielectric properties, and are not suitable for use in high-frequency electronic devices.

On the other hand, modified polyphenylene ether (PP) having a low heat resistance temperature among engineering plastics
E), polycarbonate (PC), polyethylene (PE), polypropylene (PP) and polystyrene (P
General-purpose plastics such as St) are insulative materials suitable for electronic devices utilizing high-frequency signals in that they have a low dielectric constant. However, their use environments are greatly limited due to their low heat-resistant temperatures. Therefore, at present, there is no polymer having both heat resistance and low dielectric properties.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a low dielectric resin composition having both excellent electrical properties (low dielectric properties) and heat resistance.

[0006]

Means for Solving the Problems The present inventors have made intensive studies in view of the above circumstances, and as a result, have found that a fluorine-containing aryl ether ketone polymer which the present inventors have studied so far has a low dielectric constant. Focusing on both excellent and heat resistance, it was discovered that by using such a polymer, a resin composition having both heat resistance and low dielectric properties can be obtained, and based on this finding, the present invention It was completed.

[0007] That is, the above objects are as follows:
This is achieved by (7).

(1) The following formula (I):

[0009]

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Wherein X is a halogen atom, a lower alkyl group or a lower alkoxy group, q is an integer of 0 to 4, n is a degree of polymerization, m is an integer of 0 or 1, and R ¹ Is the following formula (II):

[0011]

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In this case, X 'represents a halogen atom, a lower alkyl group or a lower alkoxy group, q' is an integer of 0 to 4, p is an integer of 0 or 1, and R ^{2 is}
Represents a divalent aromatic group, and comprises a fluorine-containing aryl ether ketone polymer represented by the formula:

(2) The fluorinated aryl ether ketone polymer has the following formula (III):

[0014]

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Wherein n represents the degree of polymerization, m is an integer of 0 or 1, and R ¹ is the following formula (II):

[0016]

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In this case, X ′ represents a halogen atom, a lower alkyl group or a lower alkoxy group, q ′ is an integer of 0 to 4, p is an integer of 0 or 1, and R ^{2 is}
Represents a divalent aromatic group, and is represented by the formula (1).

(3) In the above formula (I), R ¹ is the following formula (IV):

[0019]

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In this case, p is an integer of 0 or 1, and R ² represents a divalent aromatic group, wherein the low dielectric resin composition according to the above (1) or (2), .

(4) In the above formula (II), R ² is the following 7 types:

[0022]

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The low dielectric resin composition according to any one of the above (1) to (3), which is any one of the above.

(5) The fluorine-containing aryl ether ketone polymer has the following formula (V):

[0025]

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Wherein n represents the degree of polymerization,
The low dielectric resin composition according to the above (1).

(6) The fluorine-containing aryl ether ketone polymer has the following formula (VI):

[0028]

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Wherein n represents the degree of polymerization,
The low dielectric resin composition according to the above (1).

(7) The fluorinated aryl ether ketone polymer has the following formula (VII):

[0031]

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Wherein n represents the degree of polymerization, and R ² represents the following seven types:

[0033]

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The low dielectric resin composition according to the above (1), which is represented by any one of the above.

(8) The following formula (VIII):

[0036]

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In this case, X ′ represents a halogen atom, a lower alkyl group or a lower alkoxy group, q ′ is an integer of 0 to 4, p is an integer of 0 or 1, and R ^{2 is}
Represents a divalent aromatic group, and comprises a fluorine-containing aryl ether ketone polymer represented by the formula:

(9) The following formula (IX):

[0039]

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Wherein n represents the degree of polymerization, m is an integer of 0 or 1, and R ¹ is the following formula (IV):

[0041]

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In this case, p is an integer of 0 or 1, and R ² is the following 7 types:

[0043]

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Is a group represented by
A low dielectric resin composition comprising a fluorinated aryl ether ketone polymer represented by the formula:

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The present invention provides a compound represented by the following formula (I):

[0047]

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The present invention provides a low dielectric resin composition containing a fluorine-containing aryl ether ketone polymer represented by the formula (hereinafter, also simply referred to as “fluorine-containing aryl ether ketone polymer”).

Each repeating unit of the fluorine-containing aryl ether ketone polymer represented by the above formula (I) has the following formula:

[0050]

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A p-tetrafluorobenzoylene group represented by the following formula (hereinafter also referred to simply as “p-tetrafluorobenzoylene group”) and the following formula:

[0052]

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The oxyalkylene group represented by the formula (hereinafter simply referred to as "oxyalkylene group") is located at any position of the benzene ring (ortho, meta or para position, particularly preferably para position). Each has a structure that is bonded to each other and substituted or unsubstituted by X.

In the above formula (I), X represents a halogen atom such as a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, preferably a fluorine atom; a lower alkyl group such as methyl, ethyl, propyl, isopropyl and butyl. C1 to C6, preferably C1 to C4
Linear or branched alkyl groups, preferably methyl and ethyl, and their halogenated alkyl groups such as trifluoromethyl; lower alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy and butoxy; 1-6, preferably 1 carbon atom
And 4 straight-chain or branched-chain alkoxy groups, preferably methoxy and ethoxy, and halogenated alkoxy groups thereof such as trifluoromethoxy. Of these, a fluorine atom is particularly preferably used as X. As described above, X is a group substituted for a residual hydrogen atom to which the p-tetrafluorobenzoylene group and the oxyalkylene group are not bonded, and the number of bonds of X to the benzene ring, that is, the formula: The value of q in (I) is 0
-4.

In the above formula (I), m is an integer of 0 or 1, and R ¹ is the following formula (II):

[0056]

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Is a group represented by

In the above formula (II), X ′ is a halogen atom, for example, a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, preferably a fluorine atom;
For example, methyl, ethyl, propyl, isopropyl, butyl and the like have 1 to 6 carbon atoms, preferably 1 carbon atom.
Linear or branched alkyl groups, preferably methyl and ethyl, and their halogenated alkyl groups such as trifluoromethyl; lower alkoxy groups such as carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy and butoxy; A linear or branched alkoxy group having 1 to 6 atoms, preferably 1 to 4 carbon atoms, preferably a halogenated alkoxy group such as methoxy and ethoxy, and trifluoromethoxy. Among these, a fluorine atom is particularly preferably used as X ′. Further, the number of bonds of X ′ to the benzene ring, that is, the value of q ′ in the formula (II) is an integer of 0 to 4. That is, in the present invention, R ¹ is preferably
The following formula (IV):

[0059]

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Is a group represented by

In the above formulas (II) and (IV), p is an integer of 0 or 1. R ² is a divalent aromatic group, for example, o-, m- or p-phenylene, divalent naphthalene, biphenyl, anthracene, o-, m-
Or p-terphenyl, phenanthrene, dibenzofuran, biphenyl ether, biphenyl sulfone, and the following five formulas:

[0062]

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And other divalent aromatic groups. In the divalent aromatic group according to the present invention, hydrogen directly bonded to the aromatic ring may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group. Of these, the following seven:

[0064]

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The aromatic group represented by is preferably used as R ² .

Further, in the above formula (I), n represents the degree of polymerization, and is specifically 2 to 5000, preferably 5 to 500. Further, in the present invention, the fluorinated aryl ether ketone polymer may be composed of the same repeating unit or may be composed of different repeating units.In the latter case, the repeating unit is a block. It may be in the form of a shape or a random shape.

From the above description, the fluorine-containing aryl ether ketone polymer particularly preferably used in the present invention is represented by the following formula (III):

[0068]

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Is shown. Note that the above formula (I
In II), R ¹ and m are the same as defined in the above formula (I).

The method for producing the fluorinated aryl ether ketone polymer according to the present invention will be described in detail. When the fluorobenzoylene group side is fluorine and the oxyalkylene group side is a hydrogen atom, that is, the fluorinated aryl ether ketone polymer represented by the formula (I) has the following formula (VIII):

[0071]

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A polymer represented by the following formula (I):
X):

[0073]

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It is considered to be a polymer represented by the following formula:

Hereinafter, the fluorine-containing aryl ether ketone polymer represented by the formula (III) preferably used in the present invention will be described in detail.
A fluorine-containing aryl ether ketone polymer represented by
For example, a substituted compound is used as a starting material instead, or a desired substituent is introduced into a corresponding benzene ring of a product between each step or after completion of all steps in a synthesis method described below using a known method. Can be similarly prepared by those skilled in the art.

In the above formula (III), when m is 0, the following formula (V):

[0077]

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Here, n represents a degree of polymerization, and is a fluorinated aryl ether ketone polymer represented by the following formula.

In the above formula (III), m is 1
And p is 0, the following formula (VI):

[0080]

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Here, n represents a degree of polymerization, and is a fluorinated aryl ether ketone polymer represented by the following formula.

Further, in the above formula (III), when m is 1 and p is 1, the following formula (VI)
I):

[0083]

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Here, n represents the degree of polymerization, and R ² is as described above. In the above formula (VII), n represents the degree of polymerization.
0, more preferably 5 to 200.

In the present invention, the low dielectric resin composition comprises
It may be composed of a single kind of fluorinated aryl ether ketone polymer or of two or more kinds of fluorinated aryl ether ketone polymers. It is appropriately selected in consideration of characteristics. Specifically, 4F- manufactured in the following examples
PEK, 4F-PEEK, BPDE-6FBA, BPD
E-BA, BPDE-HF, BPDE-BF, BPDE
-HQ, BPDE-RS and BPDE- (3,4'-B
A combination of at least two kinds selected from the group consisting of A) is exemplified.

Alternatively, the low dielectric resin composition of the present invention comprises
In addition to the fluorinated aryl ether ketone polymer, another resin having a different structure may be blended as long as the electrical properties and heat resistance are not significantly reduced. Other resins used at this time include, for example, general-purpose resins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethyl methacrylate (PMMA), ABS resin and AS resin; polyacetate (POM), engineering plastics such as polycarbonate (PC), polyamide (PA: nylon), polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); and polyphenylene sulfide (PP)
S), thermoplastic resins such as polyethersulfone (PES), polyketone (PK), polyimide (PI), polycyclohexanedimethanol terephthalate (PCT), polyarylate (PAR) and various liquid crystal polymers (LCP), epoxy resins, Thermosetting resins such as phenolic resins and novolak resins are exemplified. When other resins are blended in the low dielectric resin composition of the present invention, the blending amount of the other resins is not particularly limited as long as the electrical properties and heat resistance are not significantly reduced. 0 to 50% by weight based on the raw materials, preferably based on all the raw materials,
0 to 30% by weight.

The fluorinated aryl ether ketone polymer according to the present invention is described, for example, in K. Kimura et al., Polymer Pre.
It is manufactured by the method described in prints, Vol. 39, No. 2, 1998.

More specifically, the method for producing the fluorinated aryl ether ketone polymer when the fluorinated aryl ether ketone polymer according to the present invention is represented by the above formula (V) or the above formula (VI) will be described below. explain.

First, 2,3,4,5,6-pentafluorobenzoyl chloride is converted into an organic solvent in the presence of a Friedel-Crafts catalyst, for example, with an alkoxybenzene such as methoxybenzene or ethoxybenzene or 4-methoxydiphenyl ether. P- (2,3,4) by a Friedel-Crafts reaction with 4-alkoxydiphenyl ether such as
5,6-pentafluorobenzoyl) alkoxybenzene or 4-alkoxy-4 ′-(2,3,4,5,6
-Pentafluorobenzoyl) diphenyl ether, and the reaction product was subjected to a dealkylation reaction to give the following formula (X):

[0090]

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However, q is an integer of 0 or 1, to obtain a 2,3,4,5,6-pentafluorobenzoyl compound represented by the following formula:

In the above-mentioned Friedel-Crafts reaction, the amount of alkoxybenzene or 4-alkoxydiphenyl ether used is preferably 0.8 to 1.2 moles per mole of 2,3,4,5,6-pentafluorobenzoyl chloride. Is 0.9 to 1.1 mol. At this time, if the amount of the alkoxybenzene or 4-alkoxydiphenyl ether used is less than 0.8 mol, an excessive amount of 2,3,4,5,6-pentafluorobenzoyl group is introduced into the alkoxybenzene or 4-alkoxydiphenyl ether. Not preferred. On the other hand, if the amount of the alkoxybenzene or 4-alkoxydiphenyl ether exceeds 1.2 mol, a large amount of unreacted alkoxybenzene or 4-alkoxydiphenyl ether remains, which is not preferable in terms of productivity.

Examples of the Friedel-Crafts catalyst effectively used in the Friedel-Crafts reaction include aluminum chloride, antimony chloride, ferric chloride, ferrous chloride, titanium tetrachloride, boron trifluoride, tin tetrachloride. , Bismuth chloride, zinc chloride, mercury chloride and sulfuric acid.
The amount of Friedel Crafts catalyst used was 2, 3,
It is 0.5 to 10 mol, preferably 1 to 5 mol, per 1 mol of 4,5,6-pentafluorobenzoyl chloride.

The organic solvent used in the Friedel-Crafts reaction must not react with the acid chloride. Examples of such an organic solvent include dichloromethane, dichloroethane, carbon tetrachloride, carbon disulfide, and nitrobenzene. The concentration of 2,3,4,5,6-pentafluorobenzoyl chloride in this organic solvent is 1 to 50% by weight, preferably 5 to 30% by weight. The reaction is carried out at a temperature of 0 to 150 ° C, preferably 0 to 100 ° C, while keeping the reaction system under stirring.

The product obtained by such a reaction is obtained by pouring water into the reaction mixture, extracting with an extractant such as dichloromethane, dichloroethane or carbon tetrachloride, separating the organic layer from the extract, and extracting the extractant. Is obtained by distillation. Further, by recrystallizing the product, if necessary, with methanol or ethanol,
It may be obtained as white crystals.

Next, the dealkylation treatment will be described below. That is, the dealkylation reaction can be performed using an acid, an alkali, or an organometallic reagent.
Reagents include, for example, hydrogen bromide, hydrogen iodide, trifluoroacetic acid, pyridine hydrochloride, concentrated hydrochloric acid, magnesium iodide etherate, aluminum chloride, aluminum bromide, boron trichloride, triiodide And boron hydroxide, potassium hydroxide and Grignard reagent. The amount of the reagent used is p- (2,3,4,
5,6-pentafluorobenzoyl) alkoxybenzene or 4-alkoxy-4 ′-(2,3,4,5,6
0.1 mol or more, preferably 0.1 to 30 mol, per 1 mol of (pentafluorobenzoyl) diphenyl ether.
Is a mole.

In the present invention, the dealkylation reaction may be carried out without a solvent or in a solvent, but is preferably carried out in a solvent in consideration of reaction efficiency and reaction control. .

[0098] In the present invention, examples of the solvent effectively used for performing the dealkylation reaction in the solvent include water, acetic acid, acetic anhydride, benzene and tetrahydrofuran. In addition, p-
(2,3,4,5,6-pentafluorobenzoyl) alkoxybenzene or 4-alkoxy-4 '-(2
The concentration of (3,4,5,6-pentafluorobenzoyl) diphenyl ether is 1 to 50% by weight, preferably 5 to 50% by weight.
30% by weight. The reaction is carried out at a temperature of 0-250C, preferably 50-200C.

Further, the thus obtained 2,3,4,5,6-pentafluorobenzoyl compound represented by the above formula (X) is treated with an organic solvent in the presence of a basic compound in an amount of 30 to By heating at a reaction temperature of 250 ° C, preferably 50 to 200 ° C, a fluorinated aryl ether ketone polymer represented by the above formulas (V) and (VI) is obtained.

As the organic solvent used in the above polymerization reaction, for example, N-methyl-2-pyrrolidinone, N, N-
Examples include polar solvents such as dimethylacetamide and methanol, and toluene. These organic solvents may be used alone or in the form of a mixture of two or more.

The concentration of the 2,3,4,5,6-pentafluorobenzoyl compound represented by the above formula (X) in the organic solvent is 5 to 50% by weight, preferably 10 to 50% by weight.
30% by weight.

When toluene or another similar solvent is used in the initial stage of the reaction, water produced as a by-product during the production of phenoxide can be removed as an azeotrope of toluene regardless of the polymerization solvent.

The basic compound used in the present invention acts to accelerate the polycondensation reaction by collecting hydrogen fluoride generated by the polycondensation reaction. Examples of such a basic compound include potassium carbonate, lithium carbonate and potassium hydroxide.

In the above-mentioned polymerization reaction, the amount of the basic compound used may be 2, 3, 4, 4 of the above formula (X).
The amount is 0.5 to 10 mol, preferably 0.5 to 5 mol, per 1 mol of the 5,6-pentafluorobenzoyl compound.

After completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation or the like, and if necessary, the distillate is washed to obtain a desired polymer. Alternatively, the polymer may be obtained by adding the reaction solution to a solvent having a low solubility of the polymer to precipitate the polymer as a solid, and separating the precipitate by filtration.

Next, when the fluorinated aryl ether ketone polymer according to the present invention is represented by the above formula (VII),
The method for producing the fluorinated aryl ether ketone polymer will be described below.

First, 2,3,4,5,6-pentafluorobenzoyl chloride is subjected to a Friedel-Crafts reaction with diphenyl ether in an organic solvent in the presence of a Friedel-Crafts catalyst to obtain the following formula (XI):

[0108]

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4,4'-bis (2,3,4,
5,6-pentafluorobenzoyl) diphenyl ether (hereinafter abbreviated as “BPDE”) is obtained.

In the above-mentioned Friedel-Crafts reaction, the amount of diphenyl ether to be used is 0.1 mol per mol of 2,3,4,5,6-pentafluorobenzoyl chloride.
It is 4 to 0.6 mol, preferably 0.45 to 0.55 mol. That is, the amount of diphenyl ether used is 0.4
If the molar ratio is less than 2,3, 2,3,3
A 4,5,6-pentafluorobenzoyl group is introduced, which is not preferable. On the other hand, if the amount of diphenyl ether exceeds 0.6 mol, unreacted diphenyl ether remains in a large amount, which is not preferable in terms of productivity.

The Friedel-Crafts catalyst effectively used in the Friedel-Crafts reaction includes aluminum chloride, antimony chloride, ferric chloride, ferrous chloride, titanium tetrachloride, boron trifluoride, tin tetrachloride. , Bismuth chloride, zinc chloride, mercury chloride and sulfuric acid.
The amount of Friedel Crafts catalyst used was 2, 3,
It is 0.5 to 10 mol, preferably 1 to 5 mol, per 1 mol of 4,5,6-pentafluorobenzoyl chloride.

As the organic solvent used in the Friedel-Crafts reaction, a solvent that does not react with acid chloride can be used. Examples of such an organic solvent include dichloromethane, dichloroethane, carbon tetrachloride, carbon disulfide, and nitrobenzene. The concentration of 2,3,4,5,6-pentafluorobenzoyl chloride in this organic solvent is 1 to 50% by weight, preferably 5 to 30% by weight. The reaction is carried out at 0 to 150 ° C., preferably 0 to 10 ° C., while maintaining the reaction system in a stirring state.
It is performed at a temperature of 0 ° C.

The product obtained by such a reaction is obtained by pouring water into the reaction mixture, extracting with an extractant such as dichloromethane, dichloroethane or carbon tetrachloride, separating the organic layer from the extract, and extracting the extractant. Is obtained by distillation. Further, by recrystallizing the product, if necessary, with methanol or ethanol,
It may be obtained as white crystals.

Further, the 4,4′-bis (2,3,4,5,5) thus obtained represented by the above formula (XI) is obtained.
6-pentafluorobenzoyl) diphenyl ether (BPDE) is reacted with an organic solvent in the presence of a basic compound in the following formula (XII):

[0115]

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However, R ² is represented by the above formulas (II) and (I)
By heating with a divalent phenol compound represented by the same formula (VI) as defined in (V), the compound represented by the above formula (VI)
A fluorinated aryl ether ketone polymer represented by I) is obtained.

In the above reaction, the reaction temperature is from 20 to 1
The temperature is 50 ° C, preferably 50 to 120 ° C. At this time, by reacting at such a low temperature, side reactions can be suppressed, and gelation of the polymer can be prevented.

Examples of the organic solvent used in the above polymerization reaction include N-methyl-2-pyrrolidinone, N, N-
Examples include polar solvents such as dimethylacetamide and methanol, and toluene. These organic solvents may be used alone or in the form of a mixture of two or more.

Further, the concentration of 4,4′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether in the organic solvent is 5 to 50% by weight, preferably 10 to 30% by weight. .

When toluene or another similar solvent is used in the initial stage of the reaction, water produced as a by-product during the production of phenoxide can be removed as an azeotrope of toluene regardless of the polymerization solvent.

The basic compound used in the present invention acts to accelerate the polycondensation reaction by collecting hydrogen fluoride produced by the polycondensation reaction, and further converts the phenol compound to a more reactive anion. It has the effect of changing. Examples of such a basic compound include, for example,
Potassium carbonate, lithium carbonate and potassium hydroxide.

In the above polymerization reaction, the amount of the basic compound used is 4,4′-bis (2,3,3
4,5,6-pentafluorobenzoyl) 1 to 20 mol, preferably 1 to 2 mol per 1 mol of diphenyl ether
10 moles.

The divalent phenol compound used in the above polymerization reaction is not particularly limited as long as it is represented by the above formula (XII), and for example, 2,2-bis (4-bidoxyphenyl)- 1,1,1,3,3
3-hexafluoropropane (hereinafter, referred to as “6FBA”), bisphenol A (hereinafter, referred to as “BA”),
9,9-bis (4-hydroxyphenyl) fluorene (hereinafter, referred to as “HF”), bisphenol F (hereinafter, referred to as “HF”)
“BF”), hydroquinone (hereinafter “HQ”), resorcinol (hereinafter “RS”) and 2- (3-oxyphenyl) -2- (4′-oxyphenyl) propane (hereinafter “3”). , 4'-BA ")
And the like. The amount of the dihydric phenol compound used is preferably 0.8 to 1.2 mol, preferably 1 mol of 4,4′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether. Is 0.9 to 1.1 mol.

After the completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation or the like, and if necessary, the distillate is washed to obtain a desired polymer. Alternatively, the polymer may be obtained by adding the reaction solution to a solvent having a low solubility of the polymer to precipitate the polymer as a solid, and separating the precipitate by filtration.

[0125]

Next, the present invention will be described in more detail with reference to examples.

In the following examples, physical properties were evaluated as follows.

The NMR spectrum was 500 MHz
( ¹ H), 125 MHz ( ¹³ C) or 470 MHz (
Recorded using a Varian Unity 500 operating at ¹⁹ F). 4,4′-Difluorobenzophenone was used as an internal standard for ¹⁹ F-NMR measurement.

The thermal stability was measured under nitrogen or air atmosphere.
Perkin-Elmer TG at a heating rate of 0 ° C./min
It measured using A7.

The intrinsic viscosity was measured at a concentration of 0.5 dL / g and a temperature of 25 ° C. using dimethylacetamide (DMAc).
The test was performed by using an Ostwald-Fenske viscometer in the apparatus.

Example 1 Synthesis of 2,3,4,5,6-pentafluoro-4'-hydroxybenzophenone 6.0 g of 2,3,4,5,6-pentafluoro-4'-methoxybenzophenone, ice Acetic acid 40 ml and 48%
30 ml of aqueous hydrogen bromide solution was supplied to a round bottom flask equipped with a condenser. The mixture was refluxed overnight and then cooled to room temperature. The product was extracted with diethyl ether, dried over magnesium sulfate, filtered and evaporated. The distillate was recrystallized from toluene, 3.7 g
(Yield 78.8%) of 2,3,4,5,6-pentafluoro-4′-hydroxybenzophenone (hereinafter referred to as “HP
BP ") as white crystals. The melting point of this product was 142-143 ° C. In addition, NMR of the crystal
The chemical shifts are shown in Table 1.

Example 2: 4-hydroxy-4 '-(2,
Synthesis of 3,4,5,6-pentafluorobenzoyl) diphenyl ether 250 equipped with dropping funnel and calcium chloride drying tube
In a three ml flask having a capacity of 3.5 ml, 3.5 g of 4-ethoxydiphenyl ether synthesized from ethyl iodide and p-phenoxyphenol in the presence of sodium hydroxide, 5.4 g of aluminum chloride and 30 ml of dry dichloroethane
Was charged. 2,3,4,5,6-pentafluorobenzoic acid and 2,3,3 synthesized from thionyl claroid
4,5,6-pentafluorobenzoyl chloride
A solution of 7 g and 10 ml of dry dichloroethane was slowly dropped into the flask with stirring. After the addition was completed, the reaction mixture was stirred at room temperature overnight. A small amount of water was added very slowly to the reaction mixture and stirring was continued for 15 minutes. The reaction mixture is then poured into 250 ml of water,
This was extracted with dichloromethane. The organic layers were collected, washed with water, dried over sodium sulfate, filtered and evaporated.
By treatment with activated carbon and recrystallization from methanol, white crystals of 4-ethoxy-4 ′-(2,3,4,5,6-pentafluorobenzoyl) diphenyl ether (hereinafter referred to as “EPDE”) were obtained (yield). 60.4%).

In a flask equipped with a condenser, add EPD
E 2.1 g, glacial acetic acid 14 ml and 48% aqueous hydrogen bromide solution 11 ml were charged. The mixture was refluxed overnight and then cooled to room temperature. The product was extracted with ether, dried over sodium sulfate, filtered and evaporated. By recrystallization from toluene, 4-hydroxy-4 ′-(2,
White crystals of 3,4,5,6-pentafluorobenzoyl) diphenyl ether (hereinafter referred to as “HPDE”) were obtained (yield: 78.8%). The melting point of HPDE is 136-
137 ° C. Table 1 shows the NMR chemical shifts of the crystals.

[0133]

[Table 1]

Example 3: 4,4'-bis (2,3,4,4
Synthesis of 5,6-pentafluorobenzoyl) diphenyl ether 6.8 g of diphenyl ether, aluminum chloride 26.
8 g and 60 ml of dry dichloroethane were added to a flask equipped with a dropping funnel and a calcium chloride (CaCl ₂ ) drying tube.
It was charged in a 50 ml three-necked flask. 2,3,4
A solution consisting of 18.5 g of 5,6-pentafluorobenzochloride and 15 ml of dry dichloroethane was slowly dropped into the flask with stirring. After dropping,
The reaction mixture was stirred overnight at room temperature. A small amount of water was added very slowly to the reaction mixture and stirring was continued for 15 minutes. Then the reaction mixture was poured into 250 ml of water and extracted with dichloromethane. The organic layers were collected, washed with water, dried over sodium sulfate, filtered and evaporated. By treatment with activated carbon and recrystallization from methanol, 4,4′-bis (2,2
White crystals of 3,4,5,6-pentafluorobenzoyl) diphenyl ether (hereinafter referred to as “BPDE”) were produced (yield 61.2%). The melting point of BPDE is 12
5-127 ° C. The NMR chemical shifts of the crystals are shown in Table 1 above.

Example 4 0.5 g of HPBP, 0.36 g of heavy potassium carbonate, 2 ml of dimethylacetamide (DMAc) and 1 ml of toluene
25 ml with Dean Stark trap, condenser, magnetic stirrer and nitrogen supply
Charged into a round bottom flask. The mixture was heated to 160 ° C. and toluene was distilled off. The mixture was refluxed for 3 hours. After cooling, the solution was poured into water containing 1% acetic acid under rapid stirring. The precipitated polymer was collected by filtration, washed with water, and dried. The yield of the obtained compound was 90%. The viscosity of this compound was 0.18 dL / g as measured in dimethylacetamide at a concentration of 0.5 g / dL at a temperature of 25 ° C. The insoluble content in dimethylacetamide was 11.5%.

Example 5 In the same manner as in Example 4 except that N-methyl-2-pyrrolidinone was used instead of dimethylacetamide, a polymer of HPBP (hereinafter referred to as "4F-
PEK "). As a result, the yield was 85%,
The viscosity was 0.23 dL / g, and the insoluble content in dimethylacetamide was 6.0%. Also, this 4F-PEK
Is shown in FIG. Examples 6 to 10 Polymers were produced in the same manner as in Example 4 except that in place of 0.5 g of HPBP, 0.5 g of HPDE was used and polymerization was performed under the conditions shown in Table 2. Table 2 shows the results.

[0137]

[Table 2]

Example 11 The procedure of Example 4 was repeated, except that 0.5 g of HPDE was used instead of 0.5 g of HPBP, and N-methyl-2-pyrrolidinone was used instead of dimethylacetamide. HPDE polymer (hereinafter, referred to as HPDE polymer)
"4F-PEEK"). As a result, the yield was 82%, the viscosity was 0.53 dL / g, and the insoluble content in dimethylacetamide was 0.2%. In addition, this 4F
The ¹⁹ F-NMR spectrum and IR spectrum of -PEEK are shown in FIGS. 1 and 4, respectively. In addition, ¹⁹ F
In the NMR spectrum, the ¹⁹ F chemical shift was 4,
4'-difluorobenzophenone = -110.1 ppm
Is shown in ppm corresponding to

Example 12 The thermal stability of 4F-PEK obtained in Example 5 and 4F-PEEK obtained in Example 11 were measured. The results shown in Tables 3 and 4 were obtained.

[0140]

[Table 3]

[0141]

[Table 4]

Examples 13 to 20 6FBA 1.2 purified by recrystallization from toluene
g (or BA 0.82 g, HF 1.25 g, BF
0.71 g, HQ 0.39 g, RS 0.39 g or 3,4'-BA 0.82 g), heavy potassium carbonate 1.48 g, DMAc 13 ml and toluene 10 m
100 ml with Dean Stark trap, condenser, magnetic stirrer and nitrogen supply
A three-necked round bottom flask was charged. Add this mixture to 16
The mixture was heated to 0 ° C., refluxed for 2 hours, and toluene was distilled off. 2.0 g of BPDE synthesized in Example 3 was added to this mixture, and polymerization was performed under the conditions shown in Table 5. After cooling, the solution was poured under rapid stirring into water containing 1% acetic acid. The precipitated polymer was collected by filtration, washed with water, and dried. Table 5 shows the results. FIG. 2 shows a ¹⁹ F-NMR spectrum of the polymer obtained in Example 14, and FIGS. 5 to 10 show IR spectra of the polymers obtained in Examples 14 to 19.
In the ¹⁹ F-NMR spectrum, the ¹⁹ F chemical shift was 4,4′-difluorobenzophenone = −110.
It is shown in ppm corresponding to 1 ppm.

[0143]

[Table 5]

Example 21 The polymer of BPDE obtained in Examples 14 to 20 (hereinafter referred to as “Polymer”)
When the thermal stability of "8F-PEKEK" was measured, the results shown in Tables 6 and 7 were obtained.

[0145]

[Table 6]

[0146]

[Table 7]

Example 22 The dielectric constant (ε) of the polymer of BPDE obtained in Examples 14 to 17 and 20 was measured at a frequency of 1 MHz at a temperature of 25 ° C. by an impedance measurement method. It is shown in Table 8 below.

[0148]

[Table 8]

[0149]

As described above, the low dielectric resin composition of the present invention is characterized by containing the fluorine-containing aryl ether ketone polymer represented by the formula (I). Therefore, the low dielectric resin composition of the present invention contains the fluorinated aryl ether ketone polymer represented by the formula (I) having excellent electrical properties (low dielectric properties) and heat resistance. It also has dielectric properties and is suitable as a coating composition or the like and for high-frequency electronic components such as wiring boards and insulating materials.

[Brief description of the drawings]

FIG. 1 ¹⁹ F of 4F-PEEK obtained in Example 11
-It is an NMR spectrum.

FIG. 2 shows the BPDE-6FBA obtained in Example 14.
^{It is a 19} F-NMR spectrum.

FIG. 3 is an IR spectrum of 4F-PEK obtained in Example 5.

FIG. 4 IR of 4F-PEEK obtained in Example 11
It is a spectrum.

FIG. 5 is an IR spectrum of BPDE-6FBA obtained in Example 14.

FIG. 6 IR of BPDE-BA obtained in Example 15
It is a spectrum.

FIG. 7 IR of BPDE-HF obtained in Example 16
It is a spectrum.

FIG. 8 IR of BPDE-BF obtained in Example 17
It is a spectrum.

FIG. 9 IR of BPDE-HQ obtained in Example 18.
It is a spectrum.

FIG. 10 shows I of BPDE-RS obtained in Example 19.
It is an R spectrum.

Claims (7)

[Claims] (1) The following formula (I): Wherein X represents a halogen atom, a lower alkyl group or a lower alkoxy group, q is an integer of 0 to 4, n represents a degree of polymerization, m is an integer of 0 or 1, and R is
¹ is the following formula (II): At this time, X ′ represents a halogen atom, a lower alkyl group or a lower alkoxy group, q ′ is an integer of 0 to 4,
p is an integer of 0 or 1, and R ² represents a divalent aromatic group. A low dielectric resin composition comprising a fluorinated aryl ether ketone polymer represented by the following formula: 2. The fluorinated aryl ether ketone polymer has the following formula (III): Here, n represents the degree of polymerization, m is an integer of 0 or 1, and R ¹ is the following formula (II): At this time, X ′ represents a halogen atom, a lower alkyl group or a lower alkoxy group, q ′ is an integer of 0 to 4,
The low dielectric resin composition according to claim 1, wherein p is an integer of 0 or 1, and R ² represents a divalent aromatic group. 3. In the formula (I), R ¹ is the following formula (I)
V): Here, p is an integer of 0 or 1, and R ² is 2
Or a divalent aromatic group.
3. The low dielectric resin composition according to item 1. 4. In the formula (II), R ² represents the following 7
Species: The low dielectric resin composition according to any one of claims 1 to 3, which is one of the following. 5. The fluorine-containing aryl ether ketone polymer has the following formula (V): The low dielectric resin composition according to claim 1, wherein n represents a degree of polymerization. 6. The fluorine-containing aryl ether ketone polymer has the following formula (VI): The low dielectric resin composition according to claim 1, wherein n represents a degree of polymerization. 7. The fluorinated aryl ether ketone polymer has the following formula (VII): Here, n represents the degree of polymerization, and R ² represents the following seven kinds: The low dielectric resin composition according to claim 1, which is represented by any one of the following.