JP3097704B2 - Polyamide imide resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide-imide resin, and more particularly, to a polyamide-imide resin having high heat resistance, excellent mechanical strength and elasticity, and low thermal expansion.

[0002]

2. Description of the Related Art Polyamide-imide resins have high heat resistance and excellent electrical properties and mechanical strength.
It is useful as an industrial material for electronic, mechanical, aviation or space parts, and is used after being formed into fibers, various substrates, films and the like.

When producing a printed wiring board as an electric or electronic component, this wiring board is immersed in a solder bath at 260 ° C. or higher or soldered at 330 ° C. or higher. However, when a conventionally known polyamideimide resin is used as a material for a substrate film or a coverlay film of a printed wiring board, the polyamideimide resin has no heat resistance at these temperatures, and these films are melted. In addition, since the polyamideimide resin has a large thermal expansion, a precise wiring board cannot be manufactured.

When the polyamide-imide resin is used as a material for reinforcing fibers, the polyamide-imide resin has an insufficient Young's modulus, resulting in insufficient elasticity of the resulting fiber.

[0005]

The object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a novel polyamideimide having high heat resistance and elasticity, excellent mechanical strength and low thermal expansion. It is to provide a resin.

[0006]

Means for Solving the Problems The polyamideimide resin of the present invention comprises a unit represented by the following general formula (I) and (I)
30 ° C. of a polyamide-imide resin containing a unit represented by I) as a repeating unit in a molecular chain and containing the polyamide-imide resin in a ratio of 0.5 g / dl. Has a logarithmic viscosity of 0.
It is characterized by being at least 30 dl / g, whereby the above object can be achieved.

[0007]

Embedded image

(R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and a and b each independently represent an integer of 0 to 4).

[0009]

Embedded image

(R ¹ , R ² , a and b are the same as above, Z represents an oxygen atom, CO or SO ₂ ,
Represents 0 or 1).

Next, the present invention will be described in detail.

The polyamide-imide resin of the present invention contains a unit represented by the above general formula (I) and a unit represented by the above (II) as a repeating unit in a molecular chain. ) And (II), R ¹ is a methyl group, R ² is a methyl group, a is 1, b is 1, Z is CO
And n is preferably 1. In addition, the unit represented by the general formula (I) and the unit represented by the formula (II) may be each one kind or two or more kinds.

Further, the content ratio of the above-mentioned general formula (I) and the above-mentioned general formula (II) in the polyamideimide of the present invention is preferably from 99/1 to 70/30 in molar ratio. When this content ratio exceeds 99/1 or is less than 70/30, the melting temperature of the polyamide-imide resin increases,
In addition, since the solubility in a solvent is deteriorated, the melt moldability and the solution moldability when processing the polyamideimide resin into a film, a fiber, or another molded product are deteriorated.

0.5 g of the polyamideimide resin of the present invention
The logarithmic viscosity at 30 ° C. of the N-methyl-2-pyrrolidone solution containing at a ratio of / dl is 0.30 dl / g or more, preferably 1.5 to 2.0 dl / g. When the logarithmic viscosity is less than 0.30 dl / g, the mechanical properties of the molded product such as a fiber and a film are significantly deteriorated.

Further, the polyamide-imide resin of the present invention comprises:
You may contain other units other than the unit represented by the said general formula (I) and the unit represented by (II).

The above polyamideimide resin can be synthesized by a conventionally known method. For example, the isocyanate method shown in FIG. 1 can be used.

In the above reaction, as the compound (IV), for example, 3,3 ', 4,4'-benzophenonetetracarboxylic anhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic anhydride Etc. are preferably used,
And, as the diisocyanate compound (V), for example, 4,4'-bis (3-tolylene) diisocyanate, 3,3'-dichloro-4,4'-diisocyanate biphenyl and the like are suitably used. The compound (IV) and the diisocyanate compound (V) may be used alone or in combination of two or more.

Further, acid components other than trimellitic anhydride (III) and compound (IV) include, for example, terephthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid, pyromellitic anhydride, 3,3 ', 4,4'-
Naphthalenetetracarboxylic anhydride, perylenedicarboxylic acid, perylenetetracarboxylic anhydride can be used. As amine components other than the diisocyanate compound (V), 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-
Tolylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4-diphenyl ether diisocyanate, p-phenylene diisocyanate, and m-phenylene diisocyanate can be used.

In the above reaction, the use ratio of trimellitic anhydride (III) and compound (IV) is preferably from 99/1 to 70/30 in molar ratio. The amount of the diisocyanate compound (V) used is preferably 0.8 to 1 equivalent to the total number of moles of the trimellitic anhydride (III) and the acid component of the compound (IV).

The solvent used in the above reaction includes
For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, sulfolane, and tetramethylurea are preferably used.

In the above reaction, the reaction temperature is 15
The reaction time is preferably 0 to 200 ° C. and the reaction time is 3 to 6 hours.

In addition to the above-mentioned isocyanate method, a diamine method shown in FIG. 2 can be used.

In the above reaction, as the compound (IV), for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic anhydride Etc. are preferably used,
And as the diamine compound (VII), for example,
3,3′-dimethyl-4,4′-diaminobiphenyl,
3,3'-Dichloro-4,4'-diaminobiphenyl and the like are preferably used. One or more compounds (IV) and diamine compounds (VII) may be used, respectively.

Further, as acid components other than trimellitic anhydride (IV) and compound (IV), for example, terephthaloyl dichloride, isophthaloyl dichloride,
4,4'-biphenyldiacid chloride, pyromellitic anhydride, 3,3 ', 4,4'-naphthalenetetracarboxylic anhydride, perylenediacid chloride, perylenetetracarboxylic anhydride can be used. As amine components other than the diamine compound (VII), 4,4′-
Diaminodiphenyl ether, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylsulfone, 3,3 '
-Diaminodiphenyl sulfone or the like can be used.

In the above reaction, the use ratio of trimellitic anhydride chloride (VI) and compound (IV) is preferably 99/1 to 70/30 in molar ratio. The amount of the diamine compound (VII) used is preferably 0.8 to 1 equivalent based on the total number of moles of the trimellitic anhydride chloride (IV) and the acid component of the compound (IV).

The solvent used in the above reaction includes:
For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, hexamethylphosphamide, tetramethylurea, sulfolane and the like are preferably used.

In the above reaction, the reaction temperature is from 0 to
The reaction time at 25 ° C. is preferably 3 to 5 hours.

In the production of the polyamideimide resin, an isocyanate method is preferably used industrially.

The polyamide-imide resin of the present invention is intended to further impart and improve various performances, functions, processability, and the like.
It can be used by appropriately mixing or reacting with other resins, fillers, additives, lubricants, stabilizers and the like. For example, low molecular weight polyfunctional epoxy compound, reaction or increase the denatured or crosslinked to strength by the multi-functional isocyanate, or denatured by mixing with the silicone resin, fluorine resin, etc., a small amount of inorganic fine particles (SiO _2, TiO ₂ , C
aCO ₃ etc.) to impart heat resistance, or improve the processability by reacting with a free radical-reactive monomer. In this case, the content of the polyamideimide resin is preferably 60% by weight or more, and particularly preferably 90% by weight or more.

The polyamideimide resin of the present invention is processed into various products depending on the purpose. For example, it is processed into various substrates, films, fibers, and the like. As the forming method, a conventionally known method can be used. For example,
Solution casting such as solution casting, dry spinning, wet spinning, and gel spinning; melt molding such as melt casting and melt spinning; and injection molding are preferably used.

As the solvent used for the solution molding, for example, dimethylformamide, dimethylacetamide, N
Polar solvents such as -methyl-2-pyrrolidone, dimethylsulfoxide and dimethylurea can be suitably used. In the above solvent, toluene, aromatic system such as xylene,
A mixture of ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and ether solvents such as ethyl cellosolve, diethylene glycol dimethyl ether and dioxane can also be used.

The molding temperature for melt molding and injection molding is preferably from 330 to 450 ° C.

The form of the molded product is not particularly limited, but may be a film (thickness of 2 to 200 μm) or a fiber (0.1 to 200 μm).
10 denier), hollow fibers, pipes, bottles and the like.

The obtained molded article can be used as an industrial material for automobiles, chemical plants, aviation, space, mechanical, electronic or electric parts and the like. In particular, it can be suitably used as a base material and a cover material of a flexible printed wiring board as an electrical insulating material, and a film can be formed directly on a metal foil such as a copper foil.

[0035]

The polyamideimide resin of the present invention, having a specific structure, has high heat resistance and elasticity, excellent mechanical strength, and low thermal expansion. These characteristics are considered to be derived from having a biphenyl group in the polyamideimide resin.

[0036]

Next, the present invention will be described with reference to examples and comparative examples.

Example 1 Trimellitic anhydride 17.29 g (0.09 mol) Benzophenone tetracarboxylic anhydride 3.22 g (0.01 mol) Vitriylene diisocyanate 26.43 g (0.1 mol) N-methyl-2 200 g of pyrrolidone The above composition was charged into a reaction vessel, and the temperature was raised to 200 ° C. over about 1 hour with stirring. Then, at 200 ° C for about 5
The reaction was completed by stirring for hours. N-methyl- containing the obtained polymer at a rate of 0.5 g / dl
The logarithmic viscosity at 30 ° C. of the 2-pyrrolidone solution is 1.8.
It was 3 dl / g.

An N-methyl-2-pyrrolidone solution of the above polyamideimide resin was cast on a 100 μm-thick polyester film having releasability. Thereafter, the polyester film was dried at 100 ° C. for 5 minutes and then at 150 ° C. for 30 minutes, and then the polyamide imide resin layer was peeled from the polyester film. This layer was further removed under reduced pressure to remove the solvent completely.
After drying at 0 ° C. for about 3 hours, a polyamideimide film having a thickness of 30 μm was obtained.

With respect to the obtained polyamideimide film, the tensile strength, elongation at break,
The Young's modulus, coefficient of thermal expansion and zero strength temperature were measured. Table 1 shows the results.

(1) Tensile Strength A polyamideimide film having a width of 15 mm, a length of 100 mm, and a thickness of 30 μm is pulled at a speed of 20 mm / min, and the strength when the film is broken is measured.

(2) Elongation at Break In the measurement of the tensile strength, the elongation of the film when the film is broken is measured, and the elongation is calculated.

(3) Young's modulus In the measurement of the tensile strength, it is calculated from the gradient at the beginning of strain.

(4) Coefficient of thermal expansion Using a TMA (thermo-mechanical analysis) apparatus, a width of 3 mm and a thickness of 3
The measurement is carried out by applying a load of 1 g weight to a 0 μm polyamideimide film and increasing the temperature at a rate of 10 ° C./min.

(5) Zero-strength temperature A polyamideimide film having a width of 5 mm and a thickness of 30 μm is wound around a metal rod having a diameter of 1 mm to heat the film, and the film falls when pulled from the lower part of the film with a load of 3 g weight. Measure the temperature at which to run.

Example 2 In Example 1, 15.37 g of trimellitic anhydride was used.
(0.08 mol) and 6.44 g (0.02 mol) of benzophenonetetracarboxylic anhydride were used to prepare a polyamideimide resin in the same manner as in Example 1. 0.5 g / d of the obtained polyamideimide resin
The logarithmic viscosity at 30 ° C. of the N-methyl-2-pyrrolidone solution contained at a ratio of 1 was 1.93 dl / g.
Further, a polyamide-imide film was prepared in the same manner as in Example 1, and the tensile strength, the elongation at break, the Young's modulus, the coefficient of thermal expansion, and the zero-strength temperature were measured. Table 1 shows the results.

Example 3 In Example 1, trimellitic anhydride was added at 13.45.
g (0.07 mol) and 9.66 g (0.03 mol) of benzophenonetetracarboxylic anhydride were used in the same manner as in Example 1 to prepare a polyamideimide resin. 0.5 g /
The logarithmic viscosity at 30 ° C. of the N-methyl-2-pyrrolidone solution containing dl was 1.86 dl / g. Further, a polyamide-imide film was prepared in the same manner as in Example 1, and the tensile strength, the elongation at break, the Young's modulus, the coefficient of thermal expansion, and the zero-strength temperature were measured. Table 1 shows the results. FIG. 3 shows an IR chart of the obtained polyamideimide film.

Example 4 Epicoat 154 was added to 90 parts by weight of an N-methyl-2-pyrrolidone solution of the polyamideimide resin prepared in Example 1.
The reaction was completed by adding 10 parts by weight (manufactured by Yuka Shell Epoxy Co., Ltd.) and heating at 120 ° C. for 2 hours with stirring. Using this reaction solution, a polyamideimide film was prepared in the same manner as in Example 1, and the tensile strength, elongation at break, Young's modulus, coefficient of thermal expansion, and zero strength temperature were measured. Table 1 shows the results.

Comparative Example 1 19.21 g (0.10 mol) trimellitic anhydride 4,4'-diphenylmethane diisocyanate
25.03 g (0.10 mol) N-methyl-2-pyrrolidone 200 g A polyamideimide resin was prepared from the above composition in the same manner as in Example 1. The logarithmic viscosity at 30 ° C. of the N-methyl-2-pyrrolidone solution containing the obtained polyamideimide resin at a rate of 0.5 g / dl is 1.03 dl.
/ G. Further, a polyamide-imide film was prepared in the same manner as in Example 1, and the tensile strength, the elongation at break, the Young's modulus, the coefficient of thermal expansion, and the zero-strength temperature were measured. Table 1 shows the results.

[0049]

[Table 1]

Table 1 shows that the polyamideimide films obtained in Examples 1 to 4 have high heat resistance and elasticity, excellent mechanical strength, and low thermal expansion.

[0051]

As is apparent from the above description, the polyamide-imide resin of the present invention has high heat resistance and elasticity, excellent mechanical strength, and low thermal expansion. It can be suitably used as industrial material such as mechanical, electronic or electric parts.
In particular, it can be suitably used as a base material and a cover material of a flexible printed wiring board and a reinforcing fiber as an electrical insulating material. Furthermore, since it is excellent in melt moldability and solution moldability, it can be easily processed into films and fibers.

[Brief description of the drawings]

FIG. 1 is a diagram showing a reaction formula of one production example of a polyamideimide resin of the present invention.

FIG. 2 is a view showing a reaction formula of another production example of the polyamide-imide resin of the present invention.

FIG. 3 is an IR chart of a polyamideimide film obtained in Example 3 of the present invention.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 73/14

Claims (1)

(57) [Claims] 1. A polyamide-imide resin containing, as a repeating unit, a unit represented by the following general formula (I) and a unit represented by (II) in a molecular chain, and 0.5 g of the polyamide-imide resin. A polyamide-imide resin in which the N-methyl-2-pyrrolidone solution containing at a ratio of / dl has a logarithmic viscosity at 30 ° C of 0.30 dl / g or more. Embedded image (R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and a and b each independently represent an integer of 1 to 4.) (R ¹ , R ² , a and b are the same as above, Z represents an oxygen atom, CO or SO ₂ , and n represents 0 or 1.)