JPH1045906A - Lowly hygroscopic glycidyloxy-containing aromatic polyamide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a glycidyloxy-containing aromatic polyamide resin having excellent heat resistance, mechanical characteristics, adhesiveness, solvent solubility and low hygroscopicity and ready for a crosslinking reaction by forming a resin comprising a plurality of types of specified repeating units and having a specified inherent viscosity. SOLUTION: This resin comprises 5-95mol% repeating units represented by formula I and 95-5mol% repeating units represented by formulas II and III, having a molar fraction of repeating units represented by formula II to the total of repeating units represented by formulas II and III of 50-100% and having an inherent viscosity of 0.1-3.0dl/g. In the formulas, R<1> is tetrafluorophenylene or a divalent decafluorocyclohexane group; and R<2> is a group represented by any one of formulas IV to VI [wherein R is a direct bond, C(CF3 )2 or a group represented by formula VII; and R<3> is H, CH3 or CF3 , provided that it is CF3 when R is a direct bond]. This resin is satisfactory in low permittivity, high transparency, low refractivity, stainproofing properties, water repellency, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-hygroscopic glycidyloxy group-containing aromatic polyamide resin, and more particularly, to a novel glycidyloxy group-containing aromatic polyamide resin having a low hygroscopic property by introducing a fluorine atom. About.

[0002]

2. Description of the Related Art Aromatic polyamide resins are not only resins having excellent heat resistance next to polyimide resins, but also resins having excellent mechanical properties, and are widely used as engineering plastics, especially as aramid fibers. ing. However, processing of this aromatic polyamide resin is limited due to poor solvent solubility, and its application is limited despite its excellent mechanical properties. However, due to the development of a new polyamide synthesis method and the development of monomers having polar groups and bulky structures that promote solvent solubility, it is possible to produce aromatic polyamide resins with excellent solvent solubility. And its application fields are opening up. In particular, reactive aromatic polyamide resins that can be complexed and modified with other resins are attracting attention not only as functional polymer materials but also as heat resistance improvers or adhesion improvers, and further development of applications Is a substrate.

[0003]

However, as described above, aromatic polyamide resins which are excellent in heat resistance, mechanical properties, adhesiveness and solvent solubility and are highly reactive, are contained in the resins. Due to its high hygroscopicity due to the amide bond, there is a problem that it cannot be used as a material for electronic parts, which is expected to have a wide application field due to its characteristics. In order to solve this problem, it has been proposed to introduce a fluorine atom which has low hygroscopicity, but in order to obtain sufficient hygroscopicity, it is manufactured using a monomer having a large amount of fluorine atoms. As a result,
Due to the fluorine atom having a low polarity, the resulting aromatic polyamide resin has a problem that the adhesiveness of the obtained aromatic polyamide resin is deteriorated and the aromatic polyamide resin cannot be used for its intended purpose.

Accordingly, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an aromatic polyamide resin with excellent heat resistance, mechanical properties, adhesiveness, and solvent solubility. An object of the present invention is to provide an aromatic polyamide resin having the property of having low hygroscopicity while having the same.

[0005]

Means for Solving the Problems As a result of diligent studies on the above-mentioned conventional problems, the present inventors have found that when polycondensing an aromatic dicarboxylic acid and an aromatic diamine to produce an aromatic polyamide resin, This aromatic diamine is a specific aromatic diamine component having a fluorine atom, and as the aromatic dicarboxylic acid component, a mixed dicarboxylic acid of a predetermined amount of a carboxylic acid having a phenolic hydroxyl group and a fluorine atom-substituted cyclohexane type or phenyl type dicarboxylic acid Using the components, after producing an aromatic polyamide resin containing a fluorine atom and a phenolic hydroxyl group, by subjecting the phenolic hydroxyl group to glycidyl etherification with epihalohydrin, an aromatic polyamide resin achieving the above object is obtained. This led to the completion of the present invention.

That is, the aromatic polyamide resin having a low hygroscopicity of the glycidyloxy group of the present invention has a repeating unit represented by the following formula (I) in an amount of 5 to 95 mol% and the following formula (II-
Repeating units 95 to 5 represented by 1) and (II-2)
And the molar fraction of the repeating unit represented by the formula (II-1) is represented by the formula (II-1) or the formula (II-2).
50 to 100% of the total of repeating units represented by
Wherein the intrinsic viscosity [η] is 0.1 to 3.0 dl / g.

[0007]

Embedded image [In the formula, R ¹ represents a tetrafluorophenylene group or a divalent decafluorocyclohexane group, and R ² represents a divalent group represented by the following formula (1), (2) or (3).

[0008]

Embedded image (Where R is a direct bond, -C (CF ₃ ) ₂ -or

Embedded image And R ³ represents a hydrogen atom, a methyl group or a trifluoromethyl group. When R is a direct bond, R ³ represents a trifluoromethyl group. Here, the intrinsic viscosity [η] is an intrinsic viscosity value obtained by an Ostwald viscometer and is defined by the following equation. The measurement was performed in a dimethylacetamide solution having a concentration of 0.5 g / dl at 30 ° C. [Η] = (1 / c) × ln (T ₁ / T ₀ ) (where T ₁ : fall time of resin solution (s), T ₀ : fall time of solvent (s), c: resin solution Concentration (g / d
l))

The glycidyloxy group-containing aromatic polyamide resin comprising the above-mentioned repeating unit of the present invention has not only low hygroscopicity but also excellent solvent solubility, excellent processability, and room temperature crosslinking, thermal crosslinking, Alternatively, it is a resin that can be photocrosslinked and has excellent heat resistance as well as adhesiveness. Furthermore, it has a feature that it can be easily compounded with another resin or compound, and that compounding can be easily performed according to the purpose.

[0010] The glycidyloxy group-containing aromatic polyamide resin containing the repeating unit of the present invention can be easily produced by performing various known condensation reactions. For example, a nylon salt method, an acid chloride method, an active esterification method, a direct method using a condensing agent, and the like can be applied. However, as in the present invention, for the production of an aromatic polyamide resin having a glycidyloxy group, an aromatic polyamide resin is synthesized by a direct method without protecting the hydroxyl group of a phenolic hydroxyl group-containing dicarboxylic acid monomer. It is preferable to adopt a method of synthesizing a phenolic hydroxyl group-containing aromatic polyamide in the presence of a condensing agent capable of conducting the reaction, and further glycidyl etherifying the hydroxyl group with epihalohydrin. A method for producing a phenolic hydroxyl group-containing aromatic polyamide resin by a direct method is described in U.S. Pat.
342,895.

First, 5-95 mol% of an aromatic dicarboxylic acid having a phenolic hydroxyl group represented by the following general formula (III) and a fluorine-substituted benzenedicarboxylic acid or a fluorine-substituted cyclohexanedicarboxylic acid 95 represented by the following general formula (IV) By directly polycondensing a dicarboxylic acid component containing 5 mol% and at least an equivalent of a fluorine atom-containing aromatic diamine component represented by the following general formula (V) in the presence of a condensing agent:

Embedded image HOOC-R ¹ -COOH (IV) H ₂ N—R ² —NH ₂ (V) (wherein, R ¹ and R ² have the same meanings as described above.) A repetition represented by the following formula (I) Unit and the following formula (II
A phenolic hydroxyl group-containing aromatic polyamide resin containing a repeating unit represented by -2) is synthesized.

[0012]

Embedded image (In the formula, R ¹ and R ² have the same meanings as described above.) As the aromatic dicarboxylic acid having a phenolic hydroxyl group represented by the above formula (III) used as a raw material, 5
-Hydroxyisophthalic acid, 4-hydroxyisophthalic acid, hydroxyterephthalic acid, 2-hydroxyphthalic acid, 3-hydroxyphthalic acid and the like. In the present invention, a plurality of these can be used in combination.

The fluorine-substituted benzenedicarboxylic acid or the cyclohexanedicarboxylic acid represented by the above formula (IV) includes tetrafluoroisophthalic acid,
Examples thereof include tetrafluoroterephthalic acid, tetrafluorophthalic acid, 1,2-dicarboxydecafluorocyclohexane, 1,3-dicarboxydecafluorocyclohexane, and 1,4-dicarboxydecafluorocyclohexane. In the present invention, a plurality of these can be used in combination.

Further, as the fluorine atom-containing aromatic diamine component represented by the formula (V), for example, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (4 -Amino-3-methylphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4 '-Diamino-2,2'-ditrifluoromethanebiphenyl, 4,4'-diaminooctafluorobiphenyl, 3,3'-diaminooctafluorobiphenyl, 1,3-diaminotetrafluorobenzene, 1,2-diaminotetrafluoro Benzene, 1,4
-Diaminotetrafluorobenzene and the like,
It is not limited to these. These can be used alone or in combination of two or more.

Examples of the condensing agent include those for performing polycondensation without protecting the phenolic hydroxyl group.
Synthesis and Reaction of Polymers ”, page 183 (issued in 1991), but from the viewpoint of ease of handling and cost, a combination of a phosphite and a pyridine derivative can be used. Can be preferably used.

The above polycondensation reaction includes N-methyl-2-pyrrolidone, dimethylacetamide, pyridine, 1,3-
In an amide solvent represented by dimethyl-2-imidazolidinone or the like, under an inert atmosphere such as nitrogen, at room temperature to
It can be carried out by stirring in a range of 160 ° C. for 30 minutes to several hours. In this reaction, if necessary, lithium chloride, calcium chloride, or the like can be added as a stabilizer.

Next, the phenolic hydroxyl group-containing aromatic polyamide resin obtained as described above is reacted in the presence of an alkali to react the phenolic hydroxyl group with epihalohydrin, thereby converting the phenolic hydroxyl group into a glycidyloxy group. The glycidyloxy group-containing aromatic polyamide resin of the present invention containing the repeating units represented by I) and formula (II-1) can be obtained.

The epihalohydrin used for the above glycidyl oxylation includes, for example, epichlorohydrin, epibromohydrin, epiiodohydrin and a combination thereof.

The alkali used for the glycidyl oxylation reaction includes alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide and the like, alkaline earth metal hydroxides, carbonates and the like. Preferred examples include sodium, sodium silicate, sodium metasilicate, tetramethylammonium hydroxide, hydrazine, pyridine and the like. The amount used is preferably equivalent to the phenolic hydroxyl group contained in the resin. The reaction between the phenolic hydroxyl group-containing aromatic polyamide resin and epihalohydrin is carried out in a solvent in which the phenolic hydroxyl group-containing aromatic polyamide resin is soluble, for example, an amide-based solvent such as N-methyl-2-pyrrolidone, dimethylacetamide, pyridine and the like. The reaction can be performed in an ether solvent such as tetrahydrofuran or a ketone solvent such as acetone at a temperature from room temperature to about 120 ° C. while removing generated water.

In the present invention, the amount of epihalohydrin used greatly affects the reaction rate of the glycidyloxylation reaction of the phenolic hydroxyl group, and the reaction rate can be changed by controlling the amount of epihalohydrin used. In the present invention, at least 50 mol% of the phenolic hydroxyl groups contained in the resin must be converted to glycidyloxy groups. However, in the present invention, the amount of the epihalohydrin used is preferably in the range of 2 to 10 times the mol of the phenolic hydroxyl group contained in the resin, whereby the phenolic hydroxyl group can be converted to the glycidyloxy group at a conversion of 100%. Can be converted.

In the glycidyloxy group-containing aromatic polyamide resin of the present invention, the content of the glycidyloxy group is preferably in the range of 5 to 95 mol%. As the content of the glycidyloxy group increases, the properties such as adhesive strength can be improved, but the hygroscopicity also increases. On the other hand, if the content is too small, the hygroscopicity can be improved, but the adhesive properties deteriorate. Therefore, it may be appropriately adjusted within the above range. In the present invention, if the dicarboxylic acid component and the diamino component are used in equimolar amounts,
Although a polymer having an average degree of polymerization of about 2 to 100 can be produced, the average degree of polymerization can be reduced by using one of the dicarboxylic acid component and the diamino component in excess. In the glycidyloxy group-containing aromatic polyamide resin of the present invention, the intrinsic viscosity [η] (3
(Measured with a 0.5 g / dl N, N-dimethylacetamide solution at 0 ° C.) must have a degree of polymerization in the range of 0.1 to 3.0 dl / g. The intrinsic viscosity is
If it is less than 0.1 dl / g, it becomes difficult to form a film having sufficient mechanical properties. 3.0 dl
If it is larger than / g, the degree of polymerization is too high, and the solubility of the solvent is deteriorated.

The glycidyloxy group-containing aromatic polyamide resin of the present invention produced as described above is mixed with a curing agent to be used as a curable resin composition. Any compound can be used as long as it reacts with a group to form a cross-link, for example, amino, polyaminoamide, acid and acid anhydride, phenol, urea, melamine, and isocyanate Type, mercaptan type, basic active hydrogen compound, imidazole type, Lewis acid and Bronsted acid type salt compounds, etc., as well as latent curing agent, photocuring agent (including photocuring initiator and photocuring catalyst) , Etc. can be used. Specific examples thereof include bis (4-aminophenyl) sulfone, bis (4-aminophenyl) methane, bis (3-amino-4-methyl-5-ethylphenyl) methane, and alkyl-substituted bis (4-aminophenyl) Methane, 1,5-diaminonaphthalene, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-1,4-phenylenediamine,
Aromatic amine curing agents such as 1,3-di (p-aminophenyl) propane and m-xylenediamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, isophoronediamine, bis (4 -Amino-3
-Methyldicyclohexyl) aliphatic amine compounds such as methane, polymethylenediamine, polyetherdiamine, polyaminoamide compounds obtained by heating and dehydrating fatty acids with polyethylene polyamine, dodecyl succinic anhydride, polyadipic anhydride, polyazerine Aliphatic acid anhydrides such as aliphatic anhydrides such as acid anhydrides, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; phthalic anhydride;
Aromatic acid anhydrides such as trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol tristrimellitate,
A phenolic compound represented by 2,2-bis (3-hydroxyphenyl) propane and bisphenol A, a latent curing agent represented by resol-type and novolak-type phenolic resins, an amino resin, a urea resin, a melamine resin, and dicyandiamide; Dihydrazines represented by dihydrazine adipate; 2-methylimidazole;
Imidazoles such as -ethyl-4-methylimidazole and 2-phenylimidazole, monoethylamines of boron trifluoride, piperidine salts of boron trifluoride, Lewis acids and Bronsted acid salts such as trifluoromethanesulfonic acid, low molecular Adducts of dimercaptan with polyepoxide, reactants of hydrogen sulfide with polyepoxide, polymercaptans such as esters of mercaptopropionic acid or mercaptoglycolic acid with polyhydric alcohols, isocyanates and blocked isocyanates, benzoin ethyl ether, benzyl Photocuring initiators such as methyl ketal, 2-ethylanthraquinone, 2,4-diethylthioxanthone, diallyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, Photo-curing accelerators represented by triphenylsulfonium tetrafluoroborate, triphenylselenium hexafluorophosphate, diphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, and the like, and combinations of these with the photocuring initiator Examples thereof include a photocuring agent such as a combination, but the present invention is not limited to these, and they can be used as a mixture.

Further, as the curing accelerator optionally used for reacting the glycidyloxy group-containing aromatic polyamide resin with the curing agent in the present invention, phosphorus-based, for example, triphenylphosphine, and / or 3
Secondary amines such as triethylamine, triethanolamine, 1,8-diazabicyclo [5,4,0] -7
-Undecene (DBU), N, N-dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-
Ethyl-4-methylimidazole, N-methylpiperazine and the like, and boron-based, for example, 1,8-diazabicyclo [5,4,0] -7-undecenium tetraphenylborate and the like can be mentioned.

The curable resin composition comprising the glycidyloxy group-containing aromatic polyamide resin of the present invention and a curing agent can be cured to obtain a cured product. The mixing ratio of the glycidyloxy group-containing aromatic polyamide resin and the curing agent can be variously selected according to the purpose of use, and in the present invention, there is no limitation,
Generally, it is preferable to mix in the range of 95: 5 to 30:70. In the present invention, there is no limitation on the method of blending these materials. However, the method can be carried out by dissolving and mixing these materials in a solvent to obtain a uniform mixture, and then removing the solvent. Examples of the solvent used for this mixing include alcohols, ketones, ethers, amides, chlorines, aromatics, etc., and mixtures thereof. Further, in order to cure the curable resin composition of the present invention, there is no limitation, and heating, light irradiation, or the like can be preferably used.

Further, the curable resin composition of the present invention comprises
Other additives can be added as needed.
For example, release agents such as natural waxes, synthetic waxes and long-chain aliphatic acids and metal salts thereof, acid amides, esters, paraffins, etc., and stress relaxation agents such as silicone rubber, nitrile rubber, butadiene rubber, polysiloxane, etc. ,
Flame retardants such as chlorinated paraffin, bromotoluene, hexabromobenzene, and antimony trichloride; coupling agents such as silane-based coupling agents, titanate-based coupling agents, and aluminum-based coupling agents; fused silica; crystalline silica; and glass Flakes, glass beads, glass balloons, talc, alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, rare earth cobalt, gold, silver, nickel, copper, zinc, lead, iron powder Inorganic fillers or conductive particles such as metal powders such as iron oxide and iron sand, graphite and carbon, coloring agents such as dyes and pigments, oxidation stabilizers, light stabilizers, coupling agents, thermoplastic resins, stress relaxation agents , Reaction diluent for epoxy resin, moisture resistance improver, thixotropic agent, diluent, defoamer, other It can be blended butter, and the like.

The glycidyloxy group-containing aromatic polyamide resin and the curable resin composition using the same according to the present invention are:
A cured product can be easily produced, and its usefulness is exhibited by using it as a surface protective agent, a coating agent, a binder, a sealant, a sealant, and the like. Furthermore, for electronic devices, it is used for coating materials for semiconductor elements, resin sealing agents, die bonding agents between semiconductor elements and supporting substrates, LSI mounting substrate materials, impregnated varnishes, prepreg binder resins, housing materials, etc. can do.

[0027]

The present invention will be described below in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 A 1-liter three-necked round-bottomed flask equipped with a mechanical stirrer, a cooling tube, a calcium chloride tube, and a nitrogen inlet tube was prepared.
1.821 g (10 mmol) of 5-hydroxyisophthalic acid and 2.401 g (1010 g) of tetrafluoroisophthalic acid
Mmol), 6.563 g (20 mmol) of 4,4'-diaminooctafluorobiphenyl, 2.02 g of calcium chloride, 0.66 g of lithium chloride, N-methyl-2
-120 ml of pyrrolidone, 6 ml of pyridine, and 12.41 g (40 mmol) of triphenyl phosphite were added, and the mixture was stirred at 120 ° C for 4 hours under a nitrogen atmosphere to synthesize an aromatic polyamide. This reaction solution was mixed with water: methanol (8:
2) The mixture was introduced into the mixture to precipitate a polymer. further,
Washing of the polymer was repeated twice with this mixed liquid and dried to obtain a phenolic hydroxyl group-containing aromatic polyamide.

The obtained phenolic hydroxyl group-containing aromatic polyamide was introduced into a 1-liter three-necked round-bottomed flask equipped with a Dean-Stark moisture meter, a reflux condenser, and a mechanical stirrer.
60 g, 40 g of benzene and 1 g of sodium hydroxide were added, and the mixture was heated to 100 ° C. and refluxed until water generated was removed. Then, the reaction vessel was cooled to room temperature, and 4 g of pyridine was added.
And then add epichlorohydrin 3.5 while stirring.
After adding g (40 mmol), the mixture was stirred and reacted for about 12 hours. The reaction solution was poured into a 4 liter water bath to obtain a crude product. Further, this was separated by filtration and washed twice with a mixed solution of water and methanol (weight ratio 1: 1) to give about 50 mol% of a repeating unit represented by the general formula (II-1).
Of a glycidyloxy group-containing aromatic polyamide resin was obtained at a yield of 92%. The intrinsic viscosity of this resin is 0.68 dl / g
(A value obtained from a viscosity measurement of a dimethylacetamide solution having a concentration of 0.5 g / dl at 30 ° C .; the same applies hereinafter).

The infrared spectrum (PERK) of this resin
IN ELMER 1600Series FTIR,
The same applies hereinafter), the absorption of C—F was observed at 845 cm ^−1, and the absorption corresponding to the carbonyl of the amide bond was 1
At 647 cm ^-1 , absorption corresponding to glycidyl ether was observed at about 3020 cm ^-1 , confirming that the obtained resin was the object resin of the present invention.

The moisture absorption of this resin was 0.9%.
The moisture absorption was determined as follows. That is, the produced resin is sealed in a desiccator containing a desiccant,
After measuring the mass with no change in mass, Na
Introducing a saturated aqueous solution of NO ₃ into a desiccator in which
After allowing the desiccator to stand until no change in mass occurred, the mass was measured and determined by the following equation. Moisture absorption = (moisture absorbed-dried mass) / (dry mass)

Example 2 As a dicarboxylic acid component and a diamine component as raw materials, 5
-Hydroxyisophthalic acid 10 mmol, 1,3-dicarboxydecafluorocyclohexane 10 mmol, and 4,4'-diaminooctafluorobiphenyl 20
Except for using mmol, the repeating unit represented by the general formula (II-1) was prepared in the same manner as in Example 1 so that about 50 mol%
Of glycidyloxy group-containing aromatic polyamide in a yield of 91
%. The observed values of the infrared spectrum were as follows. CF: 863 and 986 cm ^-1 , C = 0: 1
644 cm ^-1 , glycidyl ether: about 3020 c
m ^-1 . The intrinsic viscosity of this resin was 0.68 dl / g, and the moisture absorption was 0.9.

Example 3 As a dicarboxylic acid component and a diamine component as raw materials, 5
In the same manner as in Example 1, except that 18 mmol of hydroxyisophthalic acid, 2 mmol of 1,3-dicarboxydecafluorocyclohexane, and 20 mmol of 4,4'-diaminooctafluorobiphenyl were used, the compound represented by the general formula (II- A glycidyloxy group-containing aromatic polyamide having a repeating unit represented by 1) of about 90 mol% was obtained at a yield of 90%.
I got it. The observed values of the infrared spectrum were as follows. CF: 861 and 985 cm ^-1 , C = 0: 16
45cm ^-1, glycidyl ether: about 3020cm ^-1.
The intrinsic viscosity of this resin is 0.60 dl / g,
The moisture absorption was 1.2.

Example 4 As the raw material dicarboxylic acid component and diamine component, 5
In the same manner as in Example 1 except that 10 mmol of -hydroxyisophthalic acid, 10 mmol of tetrafluoroisophthalic acid, and 20 mmol of 4,4'-diamino-2,2'-ditrifluoromethanebiphenyl were used, the general formula ( A glycidyloxy group-containing aromatic polyamide having a repeating unit represented by II-1) of about 50 mol% was obtained at a yield of 91%.
I got it. The observed values of the infrared spectrum were as follows. CF: 770 and 843 cm ^-1 , C = 0: 16
40cm ^-1, glycidyl ether: about 3020cm ^-1.
The intrinsic viscosity of this resin is 0.54 dl / g,
The moisture absorption was 1.3.

Example 5 As the dicarboxylic acid component and the diamine component of the raw materials, 5
In the same manner as in Example 1, except that 1 mmol of -hydroxyisophthalic acid, 19 mmol of tetrafluoroisophthalic acid, and 20 mmol of 4,4'-diamino-2,2'-ditrifluoromethanebiphenyl were used, the general formula ( A glycidyloxy group-containing aromatic polyamide having a repeating unit represented by II-1) of about 5 mol% was obtained at a yield of 93%. The observed values of the infrared spectrum were as follows.
CF: 765 and 846 cm ^-1 , C = 0: 1639
cm ^-1, glycidyl ether: about 3020cm ^-1. The intrinsic viscosity of this resin was 0.56 dl / g, and the moisture absorption was 0.8.

Example 6 As the raw material dicarboxylic acid component and diamine component, 5
In the same manner as in Example 1 except that 2 mmol of -hydroxyisophthalic acid, 18 mmol of tetrafluoroisophthalic acid and 20 mmol of 4,4'-diamino-2,2'-ditrifluoromethanebiphenyl were used, the general formula ( A glycidyloxy group-containing aromatic polyamide having a repeating unit represented by II-1) of about 10 mol% was obtained at a yield of 90%. The observed values of the infrared spectrum were as follows. CF: 772 and 850 cm ^-1 , C = 0: 16
44cm ^-1, glycidyl ether: about 3020cm ^-1.
The intrinsic viscosity of this resin is 0.50 dl / g,
The moisture absorption was 1.0.

Example 7 As the dicarboxylic acid component and the diamine component as raw materials, 4
-Hydroxyisophthalic acid 10 mmol, tetrafluoroisophthalic acid 10 mmol, and 2,2-bis (4
-Amino-3-methylphenyl) hexafluoropropane was used in the same manner as in Example 1 except that the repeating unit represented by the general formula (II-1) was used in an amount of about 50.
A mole% of a glycidyloxy group-containing aromatic polyamide was obtained in a yield of 91%. The observed values of the infrared spectrum were as follows. CF: 765 and 840 cm ^-1 , C =
0: 1640 cm ^-1 , glycidyl ether: about 3020
cm ^-1 . The intrinsic viscosity of this resin is 0.55 dl / g
And the moisture absorption was 1.3.

Example 8 As the dicarboxylic acid component and the diamine component of the raw materials, 4
-Hydroxyisophthalic acid 10 mmol, 1,3-dicarboxydecafluorocyclohexane 10 mmol, and 2,2-bis (4-amino-3-methylphenyl)
Except for using 20 mmol of hexafluoropropane,
In exactly the same manner as in Example 1, a glycidyloxy group-containing aromatic polyamide having a repeating unit represented by the general formula (II-1) of about 50 mol% was obtained at a yield of 92%. The observed values of the infrared spectrum were as follows. CF: 761 and 985 cm ^-1 , C = 0: 1645 cm ^-1 , glycidyl ether: about 3020 cm ^-1 . The intrinsic viscosity of this resin was 0.54 dl / g, and the moisture absorption was 1.2.

Example 9 As the raw material dicarboxylic acid component and diamine component, 4
Example 1 with the exception that 4 mmol of hydroxyisophthalic acid, 16 mmol of 1,3-dicarboxydecafluorocyclohexane and 20 mmol of 2,2-bis (4-amino-3-methylphenyl) hexafluoropropane were used. By exactly the same method, a glycidyloxy group-containing aromatic polyamide having a repeating unit represented by the general formula (II-1) of about 20 mol% was obtained at a yield of 89%. The observed values of the infrared spectrum were as follows. C-F: 775 and ^{981cm -1, C = 0: 1639cm} -1, glycidyl ether: about 3020cm ^-1. The intrinsic viscosity of this resin was 0.57 dl / g, and the moisture absorption was 0.9.

Example 10 As the raw material dicarboxylic acid component and diamine component, 4
Examples 1 and 2 except that 8 mmol of -hydroxyisophthalic acid, 12 mmol of 1,3-dicarboxydecafluorocyclohexane and 20 mmol of 2,2-bis (4-amino-3-methylphenyl) hexafluoropropane were used. By exactly the same method, a glycidyloxy group-containing aromatic polyamide having a repeating unit represented by the general formula (II-1) of about 40 mol% was obtained at a yield of 90%. The observed values of the infrared spectrum were as follows. CF: 770c
m ^-1 , C = 0: 1646 cm ^-1 , glycidyl ether:
About 3020 cm ^-1 . The intrinsic viscosity of this resin is 0.5
It was 8 dl / g and the moisture absorption was 1.0.

Example 11 As the dicarboxylic acid component and the diamine component of the raw materials, 3
Example 1 except that 8 mmol of -hydroxyphthalic acid, 12 mmol of 1,4-dicarboxydecafluorocyclohexane and 20 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane were used. By exactly the same method as described above, a glycidyloxy group-containing aromatic polyamide having a repeating unit represented by the general formula (II-1) of about 40 mol% was obtained at a yield of 94%. The observed values of the infrared spectrum were as follows. CF: 774
And 991 cm ^-1 , C = 0: 1646 cm ^-1 , glycidyl ether: about 3020 cm ^-1 . The intrinsic viscosity of this resin was 0.55 dl / g, and the moisture absorption was 1.3.

Example 12 As the dicarboxylic acid component and the diamine component of the raw materials, 3
-Hydroxyphthalic acid 10 mmol, 1,4-dicarboxydecafluorocyclohexane 10 mmol, and 1,3-diaminotetrafluorobenzene 20 mmol were used in the same manner as in Example 1 to obtain the compound represented by the general formula (II)
A glycidyloxy group-containing aromatic polyamide having a repeating unit represented by -1) of about 50 mol% was obtained at a yield of 89%. The observed values of the infrared spectrum were as follows.
CF: 845 and 980 cm ^-1 , C = 0: 1645
cm ^-1, glycidyl ether: about 3020cm ^-1. The intrinsic viscosity of this resin was 0.55 dl / g, and the moisture absorption was 0.9.

Example 13 As a dicarboxylic acid component and a diamine component as raw materials, 5
A glycidyloxy group-containing aromatic polyamide was produced in exactly the same manner as in Example 1, except that 10 mmol of hydroxyisophthalic acid, 10 mmol of tetrafluoroisophthalic acid, and 20 mmol of 4,4'-diaminooctafluorobiphenyl were used. Obtained at 90%. The glycidyloxy group addition rate was 90%, and the content of the repeating unit represented by the general formula (II-1) was about 45 mol%. The intrinsic viscosity of this resin was 0.66 dl / g, and the moisture absorption was 0.8.

[0043]

The glycidyloxy group-containing aromatic polyamide resin of the present invention contains a large amount of fluorine atoms.
It has excellent low moisture absorption, and is also excellent in heat resistance, mechanical properties, and adhesiveness. Furthermore, since it has a glycidyloxy group, it can be easily crosslinked and reacted with other compounds. Further, there is an advantage that the crosslinking can be performed by heat or light. The glycidyloxy group-containing aromatic polyamide resin of the present invention is not only low in moisture absorption, but also excellent in low dielectric property, high transparency, low refractive index, antifouling property, water repellency, etc., and coating of electronic parts. It can be used as a material, wiring board material, sealing material, interlayer insulating film, optical member, and the like.

Claims (1)

[Claims] 1. A composition comprising 5-95 mol% of a repeating unit represented by the following formula (I) and 95-5 mol% of a repeating unit represented by the following formulas (II-1) and (II-2); , The molar fraction of the repeating unit represented by the formula (II-1) is 50 to 100% based on the total of the repeating units represented by the formulas (II-1) and (II-2), and the intrinsic viscosity [ η] is 0.1 to 3.0 dl / g. Embedded image [In the formula, R ¹ represents a tetrafluorophenylene group or a divalent decafluorocyclohexane group, and R ² represents a divalent group represented by the following formula (1), (2) or (3). Embedded image (Where R is a direct bond, -C (CF ₃ ) ₂ -or And R ³ represents a hydrogen atom, a methyl group or a trifluoromethyl group. When R is a direct bond, R ³ represents a trifluoromethyl group. )]