JP2005179542A - Crosslinked polyetherketone resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin having a low dielectric constant and a low dielectric loss tangent in combination with heat resistance. <P>SOLUTION: The crosslinked polyetherketone resin is obtained by introducing and bonding a tri-valent group represented by general formula (2) [wherein, R17-R19 are each a 1-8C hydrocarbon group or a divalent group represented by one formula in formulas (3)] and having a triazine ring to a polyetherketone main chain having a repeating structural unit represented by general formula (1) (wherein, A is a 1-10C divalent hydrocarbon group, -SO<SB>2</SB>-, -SO-, -S-, -O- or -CO-; m is an integer of 0 or 1; n is an integer of 1-3; R1 to R16 are each independently a hydrogen atom, a 1-8C hydrocarbon group or a halogen atom, with the proviso that at least one of R1 to R8 is a group except the hydrogen group). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a crosslinked polyetherketone resin exhibiting characteristics excellent in low dielectric constant, low dielectric loss tangent and heat resistance.

  In recent years, in the information / communication equipment field, transmission information has a high capacity and high frequency for high-speed processing. Until now, high-frequency signals exceeding GHz have been used for limited applications such as radar and satellite communications, but recently, they have become very close to mobile phones and wireless LANs. In addition, with the increase in speed and functionality of computers and communication devices, signals used for information transmission between these devices have also dramatically increased in frequency. Conventionally, epoxy resins and phenol resins have been mainly used as substrate materials used for printed wiring boards. However, these resins cannot be used for high-frequency printed wiring boards because of their poor dielectric characteristics in the high-frequency region and large transmission loss.

In addition, although inorganic substrate materials such as ceramic and alumina generally have a low dielectric loss tangent, replacement with organic materials is progressing from the viewpoints of handleability, availability and cost. Under such circumstances, there is a strong demand for the development of substrate materials that have excellent electrical characteristics (high-frequency transmission characteristics, low dielectric characteristics) that can be used in the GHz range, and polyphenylene ether resins and bismaleimide triazine resins have been developed and put to practical use. It was. (See Non-Patent Document 1 and Patent Document 1). However, the frequency of signals has increased from several GHz to several tens of GHz, and even these new materials are reaching an area that cannot be handled. Under such circumstances, development of a resin material having a low dielectric constant, a low dielectric loss tangent and excellent heat resistance as a substrate material that can be used at a higher frequency is awaited.
High frequency polymer material, CMC Co., Ltd., issued in 1999 Japanese Patent Publication No.52-31279

  The problem to be solved by the present invention is to provide a resin having both a low dielectric constant, a low dielectric loss tangent and heat resistance. More specifically, it is to provide a resin having both a low dielectric constant, a low dielectric loss tangent, and heat resistance, which can be an insulating film material for a wiring board corresponding to transmission of a high-frequency signal.

  As a result of diligent research to solve the above-mentioned problems, the present researchers have introduced a polyether ketone resin by introducing a specific structure, specifically, a trivalent crosslinking group structure containing a triazine ring into the polyether ketone structure. The present invention has been completed by finding that the resin can have a low dielectric constant and low dielectric loss tangent while maintaining the heat resistance of the resin.

That is, this invention is specified from the matter described in the following [1] and [2].
[1] A trivalent group having a triazine ring represented by the following general formula (2) was introduced into and bonded to the polyether ketone main chain having a repeating structural unit represented by the following general formula (1). A crosslinked polyetherketone resin characterized by that.

(In the formula, A represents a divalent hydrocarbon group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, or —CO—. M is an integer of 0 or 1) , N represents an integer of 1 to 3. R1 to R16 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a halogen atom, provided that at least one of R1 to R8 Is a group other than a hydrogen atom.)

(In the formula, R17 to R19 each independently represents a hydrocarbon group having 1 to 8 carbon atoms or a divalent group represented by any one of the following formula (3).)

[2] A crosslinked polyetherketone resin is represented by the following general formula (4)

(In the formula, each of R1 to R8 independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a halogen atom, and at least one of R1 to R8 is a group other than a hydrogen atom. And represents an integer of 0 or 1. A represents a divalent hydrocarbon group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, or —CO—.
And the alkali metal salt thereof represented by the following general formula (5)

(In the formula, R9 to R16 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a halogen atom. N represents an integer of _{1 to 3.} X ₁ and X ₂ represent a halogen atom. And may be the same or different from each other)
And a dihalide compound represented by the following general formula (6)

(In the formula, R17 to R19 each independently represent a hydrocarbon group having 1 to 8 carbon atoms or a divalent group represented by any one of the following formula (7). X _{3 to} X ₅ are halogen atoms. Represents an atom and may be the same or different from each other.)

The crosslinked polyether ketone resin according to claim 1, which is obtained by reacting, as a monomer, a trivalent halide compound having a triazine ring represented by the formula:

  According to the present invention, it has become possible to provide a novel crosslinked polyetherketone resin which has characteristics of low dielectric constant, low dielectric loss tangent and high heat resistance and is extremely useful for various insulating films for wiring boards.

Hereinafter, the present invention will be described in detail.
The crosslinked polyether ketone resin of the present invention has a trivalent group having a triazine ring represented by the general formula (2) on the polyether ketone main chain having the repeating structural unit represented by the general formula (1). It is a crosslinked polyether ketone resin characterized by being introduced and bonded.

In the general formula (1) of the present invention, A is a divalent hydrocarbon group having 1 to 10 carbon _{atoms, -SO 2 -, - SO -} , - S -, - O-, or especially if -CO- It is not limited. As a C1-C10 bivalent hydrocarbon group, a methylene group, ethylene group, a propylene group etc. are mentioned as an example, and a methylene group and a propylene group are especially preferable.

  In the general formula (1) of the present invention, R1 to R16 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a halogen atom, and at least one of R1 to R8 is The group is not particularly limited as long as it is a group other than a hydrogen atom. In the general formula (1) of the present invention, preferred examples of R1 to R16 include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a hydrocarbon group having 4 to 8 carbon atoms, and the like. Can be mentioned. In the general formula (1) of the present invention, m is not particularly limited as long as m is an integer of 0 or 1, and n is an integer of 1 to 3.

  In the general formula (2) of the present invention, R17 to R19 are not particularly limited as long as they are either a hydrocarbon group having 1 to 8 carbon atoms or a divalent group represented by the formula (3). Examples of the hydrocarbon group having 1 to 8 carbon atoms include a methylene group, an ethylene group, and a propylene group.

  In addition to the repeating structural unit component having the structure represented by the general formula (1), the crosslinked polyetherketone resin of the present invention contains various diol compounds and dihalide compounds with various physical properties such as heat resistance, hygroscopicity, and thermal expansion coefficient. In order to control the dielectric constant, refractive index or birefringence, etc., it may be copolymerized as necessary. However, the crosslinked polyetherketone resin having the structure represented by the general formula (1) is contained in all resins. 5 to 100% by mass, and more preferably 10 to 100% by mass is preferable.

  The crosslinked polyether ketone resin of the present invention may be produced by any method, but as an example of a preferred production method, a bisphenol compound or an alkali metal salt thereof, a dihalide compound and a trivalent ring having a triazine ring. Although the method of making it react with a halide compound is mentioned, it is not restricted to this. More specifically, the bisphenols represented by the general formula (4) and / or the alkali metal salts thereof, the dihalide compounds represented by the general formula (5), and the general formula (6) A method of producing a trivalent halide compound having a triazine ring represented by batch charging into a reaction vessel and reacting by heating from about 100 ° C. to about 300 ° C. while stirring in an organic solvent. Can be mentioned.

  Examples of bisphenols represented by the general formula (4) that can be used for producing the crosslinked polyetherketone resin of the present invention include bis (4-hydroxy-3,5-dimethylphenyl) methane, 2,2 -Bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfoxide, bis (4-hydroxy-3,5-dimethylphenyl) sulfide, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ketone, 4,4′-dihydroxy −3,3 ′, 5,5′-tetramethylbiphenyl, 1,1-bis (4′-hydroxy-3 ′, 5′-dimethyl) Butylphenyl) cyclohexane, and the like. These may be used alone or in combination of two or more. Of these, bis (4-hydroxy-3,5-dimethylphenyl) methane and 2,2-bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane are particularly preferred.

  In producing the crosslinked polyetherketone resin of the present invention, since the bisphenols react with each other by forming an alkali metal salt, the alkali metal salts of these bisphenols can be used instead. Examples of the alkali metal forming the salt include sodium and potassium, but are not limited thereto. The bisphenols may be all alkali metal salts or some alkali metal salts.

  Examples of the dihalide compound represented by the general formula (5) that can be used for producing the crosslinked polyetherketone resin of the present invention include bis (4-bromophenyl) ketone, bis (4-chlorophenyl) ketone, Or bis (4-fluorophenyl) ketone etc. can be mentioned. These may be used alone or in combination of two or more. Of these, bis (4-fluorophenyl) ketone is particularly preferred.

  Examples of the trivalent halide compound having a triazine ring represented by the general formula (6) that can be used for producing the crosslinked polyetherketone resin of the present invention include 2,4,6-tris (p- Chlorophenyl) -s-triazine, 2,4,6-tris (p-bromophenyl) -s-triazine, and the like. These may be used alone or in combination of two or more.

  There are no particular restrictions on the method for synthesizing the trivalent halide compound having a triazine ring represented by the general formula (6) that can be used in the production of the crosslinked polyetherketone resin of the present invention. Add p-halobenzonitrile to chlorosulfonic acid bathed and kept at 0 ° C. while paying attention to the temperature rise, and then add it at room temperature for about 1 to 120 hours, preferably about 24 to 120 hours. It can be obtained by reacting.

  In the production of the crosslinked polyetherketone resin of the present invention, the copolymerization ratio of the trivalent halide compound having a triazine ring and the dihalide compound is not particularly limited, but if necessary, a trivalent halide containing a triazine ring is used. The copolymerization ratio of the compound may be adjusted. When adjusting the copolymerization ratio, the molar fraction of the trivalent halide compound having a triazine ring with respect to the total number of moles of the dihalide compound and the trivalent halide compound having a triazine ring is preferably 0.1 to 20 mol%, 1-10 mol% is more preferable. If it is within this range, the effect on the low dielectric constant and low dielectric loss tangent is high, and the formed resin is stable and preferable.

The amount ratio of various compounds used as a raw material can be set according to the copolymerization ratio and molecular weight of the resin to be produced. If the amount used is bisphenol and / or alkali metal salt thereof: M ₁ mol, benzophenone dihalide compound: M ₂ mol, trivalent halide compound containing triazine ring: M ₃ mol, bisphenol and / or its The use amount ratio of the alkali metal salt to the total halide compound, M ₁ / (M ₂ + M ₃ ) is preferably in the range of 0.70 to 1.20, more preferably in the range of 0.75 to 1.15.

  In producing the crosslinked polyetherketone resin of the present invention, an end-capping agent can be used as necessary. Although the compound used as a terminal blocker is not specifically limited, A typical thing is a phenolic compound or its alkali metal salt, and a halide compound. Examples of phenolic compounds include phenol, 4-tert-butylphenol and alkali metal salts thereof. Examples of the halide compound include methyl chloride, ethyl chloride, 4-chlorobenzophenone, 4-chloronitrobenzene and the like. Generally, any one of the phenolic compounds of the end-capping agent or the alkali metal salts and halide compounds thereof may be used, but two or more of them may be used in combination depending on the purpose.

  If the amount of the end-capping agent used is too large, the molecular weight decreases, which may be undesirable in the resin film-forming property. Generally, the range of 10 mol% or less is preferable among all the raw material compounds, and the range of 5 mol% or less is more preferable.

The production of the crosslinked polyetherketone resin of the present invention can be carried out without using a solvent, but it is particularly preferable to carry out the reaction in an organic solvent. The solvent used in this reaction is not limited, but for example,
(A) a phenolic solvent,
Phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 -Xylenol, 3,4-xylenol, 3,5-xylenol,
(B) an aprotic amide solvent,
N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotri Amide,
(C) an ether solvent,
1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane ,

(D) an amine solvent,
Pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine,
(E) other solvent,
Dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole, water, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p -Dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromo Toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentane, hexane, Heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, fluorobenzene, methyl acetate, ethyl acetate, butyl acetate, methyl formate, ethyl formate and the like. Of these, dimethyl sulfoxide and N-methyl-2-pyrrolidone are preferably used. These solvents may be used alone or in combination of two or more.

  In producing the crosslinked polyetherketone resin of the present invention, an azeotropic solvent can be used as needed in addition to the above solvent for the purpose of removing water in the reaction system. Examples of the azeotropic solvent include benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene and the like. In dehydration using an azeotropic solvent, water is preferably distilled together with the azeotropic solvent, the distillate is cooled using a cooler, and water and the azeotropic solvent are preferably separated into two layers. The separated azeotropic solvent can be refluxed again to the reaction system.

  In producing the crosslinked polyetherketone resin of the present invention, a base may be present in the presence of an alkali metal salt of a bisphenol. Specific examples include alkali metal compounds represented by potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and the like. These bases may be used alone or in combination of two or more. The amount of the base used is monovalent, and is preferably 200 to 300 mol% with respect to the bisphenol, and preferably 100 to 150 mol% in the case of divalent.

  In producing the crosslinked polyetherketone resin of the present invention, the polymerization temperature and the polymerization time vary depending on the presence or type of the solvent used, but generally about 100 to 300 ° C, about 1 to 120 hours is sufficient. . In terminating the polymerization reaction, it is usually sufficient to cool the reaction product, but the end-capping agent may be added and reacted as necessary. Moreover, you may dilute by adding an inert solvent suitably before and after cooling. A known method can be used for separation and purification of the resin after completion of the polymerization reaction. The inorganic salt can be removed by adding a solvent in which the resin is soluble and the inorganic salt is insoluble to the reaction mixture, and the inorganic salt can be filtered off.

  For separation of the resin, a method is generally used in which the obtained resin solution is poured into a poorly stirred poor solvent to precipitate the resin. Examples of the poor solvent include methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, toluene, water and the like. These may be used alone or in combination of two or more. The precipitated resin may be heat-dried under normal pressure or reduced pressure. Although drying conditions depend on the kind of the poor solvent used, it is generally carried out in the range of room temperature to about 400 ° C. and about 1 minute to 100 hours. When drying under normal pressure, it is more preferably carried out in an inert gas atmosphere such as nitrogen or argon.

  The molecular weight of the polyetherketone resin of the present invention is not particularly limited, but if the molecular weight is too low, when used as a sheet for a printed wiring board material, the film forming property may not be preferable, and the molecular weight is too high. In some cases, the processing of the resin is not preferable. As a preferable molecular weight, the logarithmic viscosity ηinh measured in N-methyl-2-pyrrolidone at 35 ° C. is in the range of 0.1 to 1.5, more preferably in the range of 0.2 to 1.3, More preferably, it is the range of 0.3-1.2.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by this. Each evaluation method in the examples is shown below.

  Dielectric constant and dielectric loss tangent: The dielectric constant and dielectric loss tangent at 12 GHz were measured by the cavity resonator method.

  Glass transition temperature (Tg): Measured by DSC (Differential Scanning Calorimeter, Shimadzu DSC-60) from 25 ° C. to 400 ° C. at a heating rate of 10 ° C./min.

  5% weight loss temperature (Td 5%): Measured in air from 25 ° C. to 800 ° C. at a rate of temperature increase of 10 ° C./min with TGA (Thermogravimetric apparatus, Shimadzu Corporation TGA-50)

  Logarithmic viscosity (ηinh): 0.50 g of polyetherketone resin was dissolved in 100 ml of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) and then measured at 35 ° C. with an Ubbelohde viscometer. Note that Lauda PVS1 was used as the control unit.

  Elemental analysis: Quantified with CHN elemental analyzer (PE2400-II type).

IR spectrum: The polymer to be measured was sampled by the KBr tablet method, and spectrum measurement was performed using a Fourier transform infrared spectrophotometer (FTS6000, manufactured by Digilab Japan) at a resolution of 4 cm ⁻¹ and 128 times of integration.

Synthesis example 1
Synthesis of 2,4,6-tris (p-chlorophenyl) -s-triazine A 100 ml three-necked reaction vessel equipped with a stirrer, nitrogen inlet tube and thermometer was charged with 80 ml of chlorosulfonic acid under a nitrogen atmosphere. The temperature of the solution was kept at 0 ° C. in an ice-water bath. While stirring the solvent, 55.02 g (0.4 mol) of p-chlorobenzonitrile was added in portions while paying attention to the rise in the solution temperature. After the entire amount was put in the ice water bath, the mixture was stirred for 1 hour, and the ice water bath was further added. After removal, the mixture was stirred at room temperature for 24 hours. The progress of the reaction was observed with a high performance liquid chromatography apparatus (HPLC), and it was confirmed that the peak of the raw material was 1% or less. The resulting yellow opaque suspension was added dropwise to ice water in small portions to precipitate the reaction product, neutralized with an aqueous sodium hydroxide solution, and the precipitate was filtered off. The precipitate was washed with ion-exchanged water and methanol, filtered and dried to obtain 45.8 g (83%) of 2,4,6-tris (p-chlorophenyl) -s-triazine, which was the target product.

Example 1
In a 100 ml three-necked reaction vessel equipped with a stirrer, a nitrogen inlet tube and a thermometer, 7.68 g (0.027 mol) of tetramethylbisphenol A, 5.89 g (0.027 mol) of difluorobenzophenone and 2,4,6- Tris (p-chlorophenyl) -s-triazine (1.23 g, 0.003 mol) and potassium carbonate (4.10 g, 0.0033 mol) were charged, DMSO (60 ml) and toluene (35 ml) were added, and the mixture was stirred in a nitrogen atmosphere for 30 minutes. This was heated and reacted at 160 ° C. for 6 hours. The water produced during the reaction and azeotroped with toluene was continuously extracted while being appropriately extracted. After cooling, the reaction solution was poured into a 1: 1 mixed solvent of acetone / ion exchange water that was vigorously stirred, and polymer powder was precipitated, filtered, and further washed twice with ion exchange water and once with methanol. By the above method, white polymer powder was obtained (ηinh: 0.420 dl / g). As a result of elemental analysis of this polymer, carbon was 81.1%, hydrogen was 5.7%, and nitrogen was 0.6%. In the IR spectrum, peaks characteristic of the triazine compound, 1521 cm ⁻¹ and 1370 cm ⁻¹ were observed. From these, it was confirmed that the triazine compound was incorporated into the polymer.

Glass transition temperature: 205 ° C
5% weight loss temperature: 448 ° C
3 g of the obtained polymer powder was tableted with a compression press and then heated and compressed at 300 ° C. and 15 MPa for about 7 minutes using a hot press. The dielectric constant and dielectric loss tangent were measured using the obtained press sheet of about 0.5 mm. The results are shown in Table 1.

Example 2
The amount charged was 6.40 g (0.0225 mol) of tetramethylbisphenol A, 4.91 g (0.0225 mol) of difluorobenzophenone and 1.86 g (0.0045 mol) of 2,4,6-tris (p-chlorophenyl) -s-triazine. ), Except that it was 3.44 g (0.0248 mol) of potassium carbonate, and a reaction was carried out in the same manner as in Example 1 to obtain white polymer powder (ηinh: 0.331 dl / g). As a result of elemental analysis of this polymer, carbon was 80.6%, hydrogen was 5.7%, and nitrogen was 1.0%. In the IR spectrum, peaks characteristic of the triazine compound, 1521 cm ⁻¹ and 1370 cm ⁻¹ were observed. From these, it was confirmed that the triazine compound was incorporated into the polymer.

Glass transition temperature: 190 ° C
5% weight loss temperature: 446 ° C
A press sheet was prepared in the same manner as in Example 1, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 1.

Comparative Example 1
In the same manner as in Example 1 except that 2,4,6-tris (p-chlorophenyl) -s-triazine is not used, the compound having a repeating unit represented by the formula (8) having no crosslinked structure is used. A chain polyether ketone resin was obtained. (Ηinh: 0.40 dl / g).
Glass transition temperature: 212 ° C
5% weight loss temperature: 439 ° C
A press sheet was prepared in the same manner as in Example 1, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 1.

  The crosslinked polyetherketone resin of the present invention is useful for various wiring board insulating films, and is particularly useful as a wiring board insulating film for high-frequency signal transmission.

Claims (2)

A trivalent group having a triazine ring represented by the following general formula (2) is introduced and bonded to a polyetherketone main chain having a repeating structural unit represented by the following general formula (1). Cross-linked polyether ketone resin.

(In the formula, A represents a divalent hydrocarbon group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, or —CO—. M is an integer of 0 or 1) , N represents an integer of 1 to 3. R1 to R16 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a halogen atom, provided that at least one of R1 to R8 Is a group other than a hydrogen atom.)

(In the formula, R17 to R19 each independently represents a hydrocarbon group having 1 to 8 carbon atoms or a divalent group represented by any one of the following formula (3).)

Crosslinked polyetherketone resin is represented by the following general formula (4)

(In the formula, each of R1 to R8 independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a halogen atom, and at least one of R1 to R8 is a group other than a hydrogen atom. And represents an integer of 0 or 1. A represents a divalent hydrocarbon group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, or —CO—.
And the alkali metal salt thereof represented by the following general formula (5)

(In the formula, R9 to R16 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a halogen atom. N represents an integer of _{1 to 3.} X ₁ and X ₂ represent a halogen atom. And may be the same or different from each other)
And a dihalide compound represented by the following general formula (6)

(In the formula, R17 to R19 each represent a hydrocarbon group having 1 to 8 carbon atoms or a divalent group represented by any one of the following formula (7). X _{3 to} X ₅ each represent a halogen atom; They may be the same or different from each other.)

The crosslinked polyether ketone resin according to claim 1, which is obtained by reacting, as a monomer, a trivalent halide compound having a triazine ring represented by the formula: