JP3312430B2 - Heat resistant resin and varnish containing it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyamide-imide resin and a varnish containing the same. More specifically, the present invention relates to a heat-resistant polyamideimide resin which is soluble in a solvent having a low hygroscopicity and a low boiling point and can provide a molded article having a remarkably high light transmittance, and a varnish containing the same.

[0002]

2. Description of the Related Art Polyamide-imide resins are widely used as heat-resistant fibers, films, molding materials and the like because of their excellent mechanical properties and heat resistance. However, currently used heat-resistant resins such as polyimide and polyamide imide are dissolved only in highly hygroscopic amide solvents,
Stability over time during molding was poor. Further, at the time of molding such as wet spinning, the molded product is whitened or voids are generated due to water absorbed by the solvent, and it has been difficult to bring out excellent mechanical properties inherent to polyamideimide. Furthermore, in general, products of polyimide and polyamide imide are colored dark yellow-brown, for example,
When formed into fibers or the like, there is also a disadvantage that the coloring properties are significantly restricted. In addition, the dried film after coating is also colored yellow although it is excellent in transparency,
In the field of a liquid crystal alignment film or the like where colorless transparency is required, it has not been satisfactory.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a product which is soluble in a solvent having a low boiling point and low hygroscopicity and has a remarkably high light transmittance, in addition to the inherent heat resistance of polyamideimide. To provide a polyamide-imide resin.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have accomplished the present invention. That is, the present invention provides a compound represented by the general formula (I):

[0005]

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[Wherein R ⁰ is the following general formula (1):

[0007]

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(Wherein R and R ′ may be the same or different and each represent hydrogen or an alkyl group having 1 to 4 carbon atoms) or the following general formula (2):

[0009]

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Wherein R ¹ is the following general formula (3):

[0011]

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(Wherein Q is -Q ^0- , general formula (4):

[0013]

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And the general formula (5):

[0015]

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(Wherein Q ^{0 to} Q ⁵ may be the same or different and each represents a direct bond, -CH _2- , -CH
_{2 CH 2 -, CH (CH} 3) -, C (CH 3) 2 -, C
(CF ₃ ) _2- , -O-, -S-, -SO ₂ -or -CO-).
And a polyamideimide varnish obtained by dissolving the same in a polar solvent.

R and R ′ in R ¹ , which is a group in the repeating unit (I), may be the same or different and each is hydrogen, an alkyl group having 1 to 4 carbon atoms, preferably hydrogen,
It is a methyl group.

The polyamide-imide copolymer of the present invention has the following general formula (II) in addition to the repeating unit (I):

[0019]

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[0020] (wherein, R ⁰ is as defined above, provided that the two R ⁰ is may be the same or different) and a repeating unit represented by the following general formula represented by (III):

[0021]

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[0022] (wherein, R ⁰ is as defined above) at least one selected from the repeating units represented by the main counterbore
It may be a copolymerized polyamideimide serving as a repeating unit .

The repeating unit (I) and the repeating unit (I
The molar ratio of (I) and / or (III) varies depending on the composition, but (I) :( II) and / or (II)
I) is preferably in the range of 100: 0 to 1:99.

The characteristics of the polyamideimide of the present invention are that it does not impair heat resistance, is soluble in a solvent having a low hygroscopicity and a low boiling point such as cyclohexanone, tetrahydrofuran, diglyme, has a remarkably high light transmittance, and is substantially colorless and transparent. The ability to provide products. The polyamideimide of the present invention having such characteristics improves solubility by forming an amide bond from an alicyclic and / or aromatic-aliphatic diamine or diisocyanate, and improves the solubility of a meta-bond type aromatic diamine or diisocyanate. It is obtained by improving heat resistance and mechanical properties while maintaining non-coloring and solubility by forming an imide bond.

The polyamideimide of the present invention can be produced by a conventional method such as an isocyanate method and an acid chloride method. Industrially, the isocyanate method is suitable, but the copolymerization of a meta-linked aromatic diamine and an aliphatic or aromatic-aliphatic diisocyanate is most suitable for controlling the bonding mode regularly. That is, tricarboxylic anhydride and the following general formula (IV):

[0026]

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(Wherein Q is the same as defined above), is heated and condensed with a meta-bonded aromatic diamine to form an imide bond in advance, and then to this, the following general formula (V):

[0028]

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(Wherein R and R ′ have the same meanings as described above) or an alicyclic diisocyanate represented by the following general formula (V)
I):

[0030]

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By reacting the aromatic-aliphatic diisocyanate represented by the formula (1), the polyamideimide copolymer of the present invention can be produced efficiently.

The reaction temperature is usually preferably from 50 to 200 ° C. The reaction may be performed in the presence of a catalyst, for example, a tertiary amine, an alkali metal compound, an alkaline earth metal compound, a metal such as cobalt or titanium, or an antimetal. The reaction pressure is usually normal pressure, but the reaction may be performed under pressure.

In obtaining the polyamideimide of the present invention, it is essential to use trimellitic anhydride as the acid component monomer.

Acid components which may be copolymerized in addition to trimellitic anhydride include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Undecandioic acid, dodecandioic acid, tridecandioic acid, tetradecane, isophthalic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, terephthalic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylmethane-2,4 ' -Dicarboxylic acid, diphenylmethane-3,4'-dicarboxylic acid, diphenylmethane-3,3'-dicarboxylic acid, 1,2-diphenylethane-4,4'-dicarboxylic acid, 1,2-diphenylethane-2,4 ' -Dicarboxylic acid, 1,2-diphenylethane-3,4'-dicarboxylic acid, 1,2-diphenylethane-3,3'-di Rubonic acid, 2,2-bis (4-carboxyphenyl) propane, 2- (2-carboxyphenyl) 2- (4-carboxyphenyl) propane, 2- (3-carboxyphenyl) 2- (4-carboxyphenyl) Propane, 2,2-bis (3-carboxyphenyl) propane, diphenyl ether-4,4
-Dicarboxylic acid, diphenylether-2,4-dicarboxylic acid, diphenylether-3,4-dicarboxylic acid,
Diphenyl ether-3,3-dicarboxylic acid, diphenyl sulfide-4,4-dicarboxylic acid, diphenyl sulfide-2,4-dicarboxylic acid, diphenyl sulfide-3,4-dicarboxylic acid, diphenyl sulfide-3,
3-dicarboxylic acid, diphenylsulfone-4,4-dicarboxylic acid, diphenylsulfone-2,4-dicarboxylic acid, diphenylsulfone-3,4-dicarboxylic acid, diphenylsulfone-3,3-dicarboxylic acid, benzophenone-4,4 -Dicarboxylic acid, benzophenone-2,4-
Dicarboxylic acids such as dicarboxylic acid, butane-1,2,4-
Tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, cyclobutane-1,2,3,4-tetracarboxylic acid, benzene-1,2,4,4 5-tetracarboxylic acid (pyrrometic acid), benzophenone-3,3 ', 4,4'-tetracarboxylic acid, diphenylether-3,3', 4,4'-tetracarboxylic acid, benzene-1,2,3,3 4-tetracarboxylic acid, biphenyl-3,3 ', 4,4'-tetracarboxylic acid, biphenyl-2,2', 3,3'-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid acid,
Naphthalene-1,2,4,5-tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, decahydronaphthalene-1,4,5,8-tetracarboxylic acid,
4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid,
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid, 2,7-dichloronaphthalene-1,4,4
5,8-tetracarboxylic acid, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid,
Phenanthrene-1,3,9,10-tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid,
Bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) methane, 1,1-bis (2,3-dicarboxyphenyl) ethane, 1,1-
Bis (3,4-dicarboxyphenyl) ethane, 2,2
-Bis (2,3-dicarboxyphenyl) propane,
2,3-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) sulfone,
Bis (3,4-dicarboxyphenyl) ether, cyclopentane-1,2,3,4-tetracarboxylic acid, pyrrolidine-2,3,4,5-tetracarboxylic acid, pyrazine-2,3,5,6 -Tetracarboxylic acid, thiophene-
Examples thereof include polycarboxylic acids such as 2,3,4,5-tetracarboxylic acid and 2,3,5-tricarboxycyclopentylacetic acid, and monoanhydrides and dianhydrides thereof. These are used alone or as a mixture of two or more.
The acid component which may be copolymerized is used within a range in which the object effect of the present invention can be achieved.
Or less, preferably in a range of 30% or less.

As the meta-bonding type aromatic diamine (IV) which is an essential component of the diamine component, bis [4- (3-aminophenoxy) phenyl] propane and bis [4- (3-
Aminophenoxy) phenyl] sulfone, bis [4-
(3-aminophenoxy) phenyl] hexafluoropropane, 3,3′-diaminodiphenyl sulfide,
3,3′-diaminodiphenyl sulfone, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylpropane, 3,3′-diaminodiphenylhexafluoropropane, 4,4′-bis (3-aminophenoxy) biphenyl , 2,4-tolylenediamine, 3,3'-diaminobiphenyl, metaphenylenediamine, 3,3'-
Diaminobenzanilide, 3,3′-diaminodiphenylmethane, 2,4-dimethylmetaphenylenediamine,
5-nitro-metaphenylenediamine, 5-chloro-metaphenylenediamine and the like.

The alicyclic diisocyanate (V) or aromatic-aliphatic diisocyanate (VI), which is another essential component of the diamine component, includes, for example, xylene diisocyanate, dicyclohexylmethane diisocyanate, dicyclohexylpropane diisocyanate, and the like. .

Further, as a diamine component, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, p-phenylenediamine,
Oxydianiline, methylenedianiline, hexafluoroisopropylidenedianiline, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, 2,2 ′
-Bis (4-aminophenyl) propane, 2,2'-bis (4-aminophenyl) hexafluoropropane,
4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 3,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, hexamethylenediamine, tetramethylenediamine, isophoronediamine, 5-amino-1- (4'-aminophenyl)-
1,3,3′-trimethylindane, 3,4′-diaminodiphenyl ether, isopropylidene dianiline,
4,4′-diaminocyclohexyl, o-tolidine,
2,4-tolylenediamine, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-
[1,4-phenylenebis (1-methylethylidene)]
Bisaniline, 3,3 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) ) Phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy)
Phenyl] hexafluoropropane, 4,4'-diaminodiphenylsulfide, or 6-amino-1-
(4′-Aminophenyl) -1,3,3-trimethylindane or a diisocyanate corresponding thereto may be polymerized. These can be polymerized alone or as a mixture of two or more. Diamines that may be copolymerized are used within a range that does not deteriorate the properties of the polyimideamide of the present invention, but usually, in all the diamine components,
It is 50 mol% or less, preferably 30 mol% or less.

The polyamide imide of the present invention comprises a repeating unit (I) and a repeating unit (II) and / or (II)
In the case of the copolymer (I), it may be a block copolymer of (I) and (II) and / or (II) or a random copolymer.

The optimum value of the molecular weight of the polyamideimide is also different depending on each composition and use.
0.1 to 2. logarithmic viscosity value at 30 ° C. in pyrrolidone.
The range is 5 dl / g, preferably 0.4 to 1.0 dl / g.

The molar ratio of the meta-linked aromatic diamine (part of the R ¹ component) to the alicyclic diisocyanate and / or the aromatic-aliphatic diisocyanate (part of the R ⁰ component) is as follows:
Although it depends on each composition, about 50/50 to 1/99
Is preferable. When the amount of the alicyclic diisocyanate and / or the aromatic-aliphatic diisocyanate is further increased, the solubility is excellent but the heat resistance and the mechanical properties tend to decrease.

When the polyamideimide of the present invention is used as a varnish, amide polar solvents such as dimethylformamide, dimethylacetamide, diethylacetamide, N-methyl-2-pyrrolidone and hexamethylphosphamide which are common solvents for polyamideimide are used. As well as dioxane, diglyme, ether organic solvents such as tetrahydrofuran, toluene, hydrocarbon organic solvents such as xylene, cyclohexanone, cyclopentanone, methyl ethyl ketone, which could not be dissolved in the conventional polyamideimide polymer, It is also soluble in ketone organic solvents such as methyl isobutyl ketone and other non-amide polar solvents such as isophorone, acetonitrile and γ-butyrolactone. Among them, diglyme, tetrahydrofuran and cyclohexanone are preferably used from the viewpoint of solubility or toxicity.

The ratio of the polyamide imide to the solvent is appropriately determined depending on the purpose of use and the like. Usually, the solvent is used in an amount of 100 to 3,000 parts by weight, preferably 300 to 1,000 parts by weight, per 100 parts by weight of the polyamide imide. Is done.

The polyamideimide resin of the present invention can be formed by a conventionally known method such as solution casting, dry spinning, wet spinning, gel spinning, melt spinning, melt molding, injection molding and the like. In particular, in the case of solution casting such as solution casting and dry spinning, the solvent used has a low boiling point and low hygroscopicity, so it is excellent in handleability, and the physical properties of the obtained molded product are those molded from conventional amide solvents. It is much better than.

The form of the molded article is not particularly limited, but may be a molded article such as a film, a fiber, a hollow fiber, a pipe, a bottle and the like. Although there is no particular limitation on the application, parts for automobiles, chemical plants, aerospace / mechanics, electric / electronics,
Can be used as material.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples.

[0046]

Example 1 The following polymerization components were charged into a reaction vessel and reacted at room temperature for 3 hours. Then, 70 ml of triethylamine was added and the reaction was carried out at 200 ° C. for 3 hours while removing by-produced water. Polymerization component trimellitic anhydride 1 mol bis [4- (3-aminophenoxy) phenyl] sulfone 0.5 mol N-methyl-2-pyrrolidone 0.8 l toluene 0.2 l Then 4,4'-dicyclo 0.5 mol of methane diisocyanate and 1 liter of N-methyl-2-pyrrolidone were added, and the mixture was stirred at 200 ° C. for 24 hours to stop the reaction. Then, the polyamideimide polymerization solution was diluted with N-methyl-2-pyrrolidone and then reprecipitated in methanol to obtain a polyamideimide powder.

After dissolving the above-mentioned polyamideimide powder in cyclohexanone so that the solid content concentration becomes 20% by weight, the thickness after drying on the release polyester film is 3%.
And cast at 60 ° C. for 10 minutes.
After drying at 0 ° C. for 20 minutes and at 150 ° C. for 30 minutes, the film was peeled off from the release film. Table 1 shows various physical properties of the polyamideimide film thus obtained. The measuring method of each physical property in the table is shown below. Tg (° C.): Depends on TMA tensile measurement. Load: 1 g, sample size, 5 × 20 mm Measured at a heating temperature of 10 ° C./min. Light transmittance: using a film having a thickness of 25 μm and a wavelength of 50
Measured at 0 nm Solubility: Polymer powder (diameter: 2 to 3 μm) was mixed with cyclohexanone so as to have a concentration of 20% by weight, stirred at room temperature, and visually observed. 〇: Dissolution ×: Not required

Examples 2, 3 and 4, Comparative Example 1 The procedure of Example 1 was repeated except that the aromatic diamine and diisocyanate used in Example 1 were changed to the monomers shown in Table 1. I got
Various physical properties of the obtained polyamideimide were measured in the same manner as in Example 1. Table 1 shows the results.

Example 5 The following polymerization components were charged into a reaction vessel, and reacted at room temperature for 3 hours. Then, 70 ml of triethylamine was added, and the mixture was reacted at 200 ° C. for 3 hours while removing by-produced water. Polymerization component trimellitic anhydride 0.6 mol bis [4- (3-aminophenoxy) phenyl] sulfone 0.3 mol N-methyl-2-pyrrolidone 0.8 liter toluene 0.2 liter Then, the following polymerization components were added. Then, the mixture was stirred at 200 ° C. for 24 hours to stop the reaction. Polymerization component Trimellitic anhydride 0.4 mol 4,4'-dicyclohexylmethane diisocyanate 0.7 mol N-methyl-2-pyrrolidone 1 liter The obtained polyamideimide has repeating units (I) and (I)
It was a copolymerized polyamideimide consisting of I) and (III). Using the obtained polyamideimide polymerization solution, a polyamideimide powder and a film were prepared in the same manner as in Example 1, and the physical properties were measured as in Example 1. Table 1 shows the results
Shown in

[0050]

[Table 1]

[0051]

The polyamideimide of the present invention not only dissolves in an amide-based polar solvent which is a solvent for a conventional imide-based polymer, but also has a low hygroscopicity and a boiling point such as cyclohexanone, dioxane, toluene, xylene, tetrahydrofuran and diclime. It is soluble in general-purpose solvents with low Therefore, it is excellent in solution moldability, and its coatings, fibers and other molded products are
It shows extremely high light transmission and is substantially colorless and transparent.

Continuation of the front page (72) Inventor Hideo Nishino 2-1-1 Katata, Otsu-shi, Shiga Pref. Toyo Spinning Co., Ltd. (56) References JP-A-6-345867 (JP, A) Special Table Sho56- 501883 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 CAPLUS (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] (1)More than 70 mol% of the acid component is anhydrous trimellit
Is citric acid and 70 mol% or more of the diamine component
Has the following general formula (1 ′) Embedded image  (Wherein R and R ′ may be the same or different,
Each represents hydrogen or an alkyl group having 1 to 4 carbon atoms
X represents an amino group or an isocyanate group. )so
A compound represented by the following general formula (2 ′): Embedded image  (Wherein X is as defined above) and the following:
General formula (3 ′): Embedded image  [Where Q is -Q ⁰ -, General formula (4): Embedded image  And general formula (5): Embedded image  (Where Q ⁰ ~ Q ^Five May be the same or different
Respectively, a direct bond, CH _Two -, -CH _Two CH
_Two -, CH (CH _Three )-, C (CH _Three ) _Two −, C (CF
_Three ) _Two -, -O-, -S-, -SO _Two -Or -CO
-), And X is as defined above. At least
Is also a polyamide-imide resin consisting of a kind of compound.
hand, Trimellitic acid accounts for 70 mol% or more of the acid component
And at least 70 mol% of the diamine component.
The compound represented by the general formula (1 ′) or the compound represented by the general formula (2 ′)
A compound represented by the general formula (3 ′)
Is represented by the following general formula:
(I): Embedded image  [Wherein, R ⁰ Is the following general formula (1): Embedded image  (Wherein, R and R ′ are as defined above) or the following general formula:
(2): Embedded image  And R ¹ Is the following general formula (3): Embedded image  (Wherein Q is as defined above)
Or a repeating unit represented by
Represents the repeating unit and the following general formula (II): Embedded image  (Where R ⁰ Is as defined above, provided that two R ⁰ Are the same
Or may be different).
And the following general formula (III): Embedded image  (Where R ⁰ Is the same as defined above)
Consisting of at least one type of repeating unit selected from
And, A repeating unit of the formula (I) and a repeating unit of the formula (II)
A repeating unit and / or a repeating unit of the formula (III)
Is a molar ratio of 100: 0 to 1:99.
Do Copolyamideimide. 2. The method according to claim 1, wherein the polyamideimide is polar.
Polyamideimide varnish dissolved in a solvent . 3. The method according to claim 1, wherein the polar solvent is a non-amide polar solvent.
Polyamideimide varnish Motomeko 2 wherein.