JPH0195155A - Polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyimide resin composition improved in moldability, especially, solubility, by dissolving a polyimide having specified repeating units in an organic solvent having a specified solubility parameter. CONSTITUTION:A polyimide resin composition is prepared by dissolving a polyimide having repeating units of formula I in an organic solvent having a solubility parameter sigma([cal/cm<3>]<1/2>) in the range of 9-14. In formula I, R<1> is a tetravalent organic group of formula II or III, X is a bivalent organic group of any one of formulas IV-VII, -o- or -CH2-. Said polyimide is produced by feeding substantially equimolar amounts of a tetracarboxylic acid dianhydride of formula VIII and bis(aminophenoxyphenyl)hexafluoropropane in a reactor, reacting them in an organic polar solvent at low temperature to form a polyamic acid having repeating units of formula X and imidating this polyamic acid. Examples of said organic solvent (the values in the parentheses represent sigma) of formula I include tetrahydrofuran (9.1), chloroform (9.3) and methylene chloride (9.3).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is applicable to semiconductor devices, electrical equipment such as printed circuits, optical equipment such as liquid crystal display elements, X-ray exposure masks, color filters, optical fibers, printing recording devices, The present invention relates to a polyimide resin composition useful as a coating material, film material, etc. related to information recording such as electrophotography.

[Conventional technology]

Polyimide resins have excellent mechanical, physical, chemical, and electrical properties over a wide temperature range, as well as UV protection, radiation resistance, and flame retardancy.

However, polyimide resins have extremely poor moldability, so their uses have been limited. In order to improve this moldability, improvements in the molecular structure, modification of the resin, development of molding methods, use of precursors, development of new solvents, etc. are being considered.

[Purpose of the invention]

The present inventor has made extensive studies to improve the molding processability of polyimide resin, especially the solubility of polyimide resin, without impairing the original crushed characteristics of the polyimide resin, and has invented a polyimide resin composition that can be dissolved in an extremely wide range of organic solvents. .

That is, the gist of the present invention is the general formula (1) (wherein, RI U 3 or H'l3rx13: represents an organic group with a covalent value, and X represents an organic group with a covalent value of -d-1). .) is dissolved in an organic solvent having a solubility coefficient δ ([CaVm'':]5% of 9 to /Z).

[Structure of the invention]

The present invention will be explained in more detail below.

The polyimide of the present invention is tetracarboxylic dianhydride (IV
ay I and bis(aminophenoxyphenyl)hexafluoropropane [V].

A polyamic acid having a repeating unit represented by the following general formula [■] was produced by charging approximately equimolar amounts and reacting at a low temperature in a pumped polar bath.

(R1 is the same table as above) It is produced by imidization using a conventional method.

The organic solvent which is a constituent component of the polyimide resin composition of the present invention is selected from those having a solubility coefficient b (C"'/Cm') in the range of 5% to /4t. Such solvents (in parentheses are δ ], Tetrahydrofuran (Ri,
/), chloroform (9,3), methylene chloride (
9,7), 8/, 2,2-tetrachloroethane (P,
7), cyclohexanone (?,y), /, goudioxane (10,o), nitrobenzene (70,0)
, m-cresol (10,2), diethylene glycol monoethyl ether (10,co), acetonitrile (1
0#), N,N-dimethylacetamide (10i),
N-methylpyrrolidone (//, 3), ethylene glycol monomethyl ether (//, g), acetonitrile (
//, 9), dimethyl sulfoxide (/2.o), N
, N-dimethylformamide (/2./), γ-butyrolactone (/2. O), nitromethane (/J, 7L tetramethylene sulfone (/3 reviews), etc. (The δ value is based on "Polymer Handbook J 5econd E
dition, John Wiley & 5On8 nc, /97! Annual issue P337~P3! (depending on the situation).

These solvents can be used alone or in combination. Further, a solvent having a δ value outside the above range can also be used in combination to the extent that solubility is not impaired.

Specific examples of the tetracarboxylic dianhydride represented by the formula [IV) in the present invention include, for example, 3.3',
K rating'-diphenyltetracarboxylic dianhydride, λ,
, 2',j, 3'-diphenyltetracarboxylic dianhydride, 2,3,3', nail-diphenyltetracarboxylic dianhydride, 3,3z<t, at-benzophenonetetracarboxylic dianhydride, λ, 2-bis(3゜a-dicarboxyphenyl)propanihydride, Kotsu 2-bis(a-(,
t,a-dicarboxyphenoxy)phenyl]propanihydride 1.2. ．． 2-bis[a-(Jj-dicarboxyphenoxy)phenyl]propanihydride, λ, 2-
Bi/C(3,y-dicarboxyphenyl)hexafluoroproxyanhydride, bis(3,4t-dicarboxyphenyl)sulfone dianhydride, bis(3,\-dicarboxyphenyl)ether dianhydride, bis( 3,a-dicarboxyphenyl)methane dianhydride and the like, and mixtures thereof can also be used.

The reaction between tetracarboxylic dianhydride and bis(amine phenoxyphenyl) hexafluoropropane is carried out using an organic solvent,
For example, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylglopionamide, N-methyl-2-pyrrolidone, /,! -Dimethyl-[lambda]-pyrrolidone and other pyrrolidones, phenol, p-chlorophenol, o-chlorophenol and other organic polar solvents are preferably used alone or in a mixed solvent.

The first reaction to produce polyamic acid [■1] is preferably carried out at a relatively low temperature, e.g., 50°C or lower. The dianhydride component can be added to this solution to carry out the reaction.

The polyamic acid solution thus obtained can be imidized by various methods. For example, (a) a method in which the polyamic acid solution is directly heated and dehydrated to imidize it (b) a method in which the polyamic acid solution is cast onto a glass plate, etc. and then heated and dehydrated to imidize it (c) a method in which the polyamic acid solution is heated and dehydrated to imidize it; After adding and mixing an imidization catalyst such as an acid anhydride, it is cast onto a glass plate, etc., and imidized by dehydration at room temperature or heating. , A method of heating and drying the divided powder to imidize it (f) A method of imidizing it by heating and dehydrating it at room temperature or in an imidization catalyst such as a tertiary amine and acid anhydride or an organic solvent containing them, etc. There is.

Polyamic acid in N-methylpyrrolidone
Logarithmic viscosity ηin measured at a concentration of and a temperature of 30"C
h is θ, /dl/11~/Odl/11, preferably f
; -0.3 dl/11 or more and j di / # or less is desirable.

Moreover, the polyimide of the present invention has a high molecular weight necessary for forming a film or a molded article, i.e., 0.2% in concentrated sulfuric acid.
The logarithmic viscosity ηinh measured at a concentration of Ill/di and a temperature of 0'C is 0. /di/9~10dl/9,
Preferably, j di / is in the range of 0.3d17g or more and 9 or less. Here, the logarithmic viscosity ηinh is expressed by the following formula ηinh = j; n (7ref) /C In the formula, C is the concentration of the polymer solution (1 polymer/10 Omt of solvent), and ηreJ- is the relative viscosity, that is, measured with a capillary viscometer. It is a measurement defined as the ratio of the flow times of a polymer solution and a solvent.

The polyimide of the present invention is characterized by having a repeating unit represented by the general formula [I], and may be a homopolymer or a copolymer. Furthermore, in addition to the one consisting only of the unit, a copolymer having the unit as the main component may be used. Examples of copolymerized units other than [■] include units of general formula [I] in which the amine component is replaced with another amine component, and specific examples include those derived from the following diamines. .

That is, for example, core 2-bis[gu(/lt-aminophenoxy)phenyl]propane, -, rhobis[3-methyl-a-(g-aminophenoxy)phenyl]furopane, core 2-bis(j-10rho) g(4t-aminophenoxy)phenyl]flopane, core 2-bis[3-promoy-(quaminophenoxy)phenyl]propane, 2,2-bis[3-ethyl-a-(g-aminophenoxy)phenyl] Propane, λ, 2-bis[3-propyl-a-(p-aminophenoxy)phenyl]propane, 2,2-bis[3-isopropyl-ti-(/lt-
Aminophenoxy)phenyl]propane, Co, Tubis[3-butyl-gu(4t-aminophenoxy)phenyl]propane, 2. ．． 2-bis[3-8ec-butyl-
Gu(4t-aminophenoxy)phenyl]propane 1
．． 2.2-bis(3,t-dimethyl-cou(aminophenoxy)phenyl)furopane, 2.-bis(: 3
．． t-cycloa-(4t-aminophenoxy) pheninolipropane, cot-monobis[3,j-dibromo-
X-(4t-aminophenoxy)phenyl]propane, cot-monobis[3-chloro-<t-(X-aminophenoxy)-! -methylphenyl]propane, /, /-bis[g-(4t-aminophenoxy)phenylemene,
/,/-bis[3-methyl-gu(qua-aminophenoxy)phenyl]ethane, /,/-bis[3-chloro-gu(Z-aminophenoxy)phenyl]ethane, /,/
-bis[3-furomo-a-(g-aminophenoxy)phenyl]ethane, /,/-bis[3-ethyl-Z-(teraminophenoxy)phenyl]ethane, /,/-bis[3-propyl-g (<t-aminophenoxy)phenyl]ethane, /, /-bis[3-isopropyl-a-
(4t-aminophenoxy)phenyl]ethane, /, /
-bis[3-butyl-y-(4t-aminophenoxy)
phenyl]ethane, /, /-bis(3-θec-butylrug(p-aminophenoxy)phenyl]ethane, /
,/-bis(3,!-dimethyl-gu(gu-aminophenoxy)phenyl)ethane, /,/-bis(3,j-dichloro-<t-(g-minophenoxy)phenyl]ethane, /,/-bis [3,!-dibromoe-(4t-
aminophenoxy)phenyl]ethane, /, /-bis[
3-chloro-cou(teraminophenoxy)-! -methylphenyl]ethane, bis[a-(g-aminophenoxy)phenyl)methane, bis[3-methyl-ter(4t
-aminophenoxy)phenylcomethane, bis[3-chloro-y-(4t-aminophenoxy)phenylcomethane, bis[3-promogu(4t-aminophenoxy]phenyl]methane, bis[3-ethyl-<t- (g-
Aminoneenoxy) phenylcomethane, bis[3-propyl-a-(4t-aminophenoxy)phenylcomethane, bis[3-isopropyl-a-(4t-aminophenoxy)phenylcomethane, bis[3-butyl- a-(
4t-aminophenoxy)phenylcomethane, bis(3
-5ea-butyl-gu(4t-aminophenoxy)phenylcomethane, bis(3,!-dimethyl-a-(4t
-aminophenoxy)phenylcomethane, bisC3,r
-dichloro-%-(4t-aminophenoxy)phenylcomethane, bis[3,! -dibromogu(4t-aminophenoxy)phenylcomethane, bis[3-chloro-
y-(x-aminophenoxy)=! -methylphenyl]
Methane, 3,3-bis(g-(quaminophenoxy)
phenyl]pentane, /, / -his[y-(x-aminophenoxy)phenyl]furopane, 3,3-bis[3
, r -dimethyl-a-(4t-aminophenoxy)phenyl]pentane, /, /-bis[3,! -dimethylruder(kuaminophenoxy)phenyl]propane, 3
．． 3-bis[3,terdipromoder(4t-aminophenoxy)phenyl]pentane, to/-bis[3,! −
Dibromo<t-(4t-aminophenoxy)phenyl]furopane, 2,2-bis[gu(g-aminophenoxy)phenylkobutane, 2,2-bis[3-methyl-gu(4t-aminophenoxy)phenylkobutane] 2.
2-bis[3゜r-dimethyl-<t-(p-aminophenoxy)phenylcobutane, 2.2-bis[bis(3,
Examples include t-dibromo-<t-(X-aminophenoxy)phenylcobutane.

The content of copolymerized units other than the units of the general formula CI] is 3
It is preferable that it is 0 molti or less.

The composition of the present invention can be easily produced by dissolving the polyimide produced by the above imidization method in an organic solvent having the δ value of the present invention at room temperature or by heating.

The polyimide resin composition of the present invention may contain well-known compounding agents, such as antioxidants, heat stabilizers, ultraviolet absorbers, colorants, fillers, etc., according to known formulations.

The polyimide resin composition of the present invention is not only useful as a paint (fen, coating agent), but also useful for producing molded articles such as fibers, separation layers, and films.

In particular, it is suitably used as a coating material such as a liquid crystal alignment film and a pus retaining material for a hard disk.

〔Example〕

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Similarly, the physical properties of the film were evaluated as follows.

Tensile test: AE3TM13. ? It was measured at 20°C using a method based on the test method of .

Glass transition point (hereinafter abbreviated as Tg): Measured using a thermal mechanical analyzer manufactured by Shimadzu Corporation at a heating rate of /θ°C/min.

Example / iooomty equipped with a thermometer and a stirring device: 2,2-bis[<=-(g-aminophenoxy)phenyl]hexachloropropane (hereinafter abbreviated as B A P F) 20,7771/ It was accurately weighed and dissolved by adding N,N-dimethylacetamide (hereinafter abbreviated as DMAC)/jOml. Next, 3,4t,3',4t'-biphenyltetracarboxylic dianhydride/to! 6 Otsu 1 and DMAC
I6011 was added and reacted at room temperature for 2 hours to obtain a polyamic acid solution with a weight of t%. A portion of this solution was diluted with a large amount of N-methylpyrrolidone to 0. ni f//d
When an N-methylpyrrolidone solution of i was prepared and the logarithmic viscosity was measured, it was found to be ♂dl/p. From the infrared absorption spectrum, the absorption of amic acid (NH
) was recognized.

Next, to the above polyamic acid, acetic anhydride/j,91 and isoquinoline! , θg was added and reacted at room temperature for 24 hours, then further at 20°C! It was reacted for a time and imidized. 3270 from the infrared absorption spectrum. -' amic acid absorption was not observed. The reaction product was dropped into a large amount of demineralized water to precipitate the polymer, which was then taken from house to house and thoroughly washed with methanol.

Next, 24 was dried at 110° C. under reduced pressure for an hour to obtain polyimide powder.

Dissolve this polyimide powder in N-methylpyrrolidone,
When a solution of 0.6117 di was prepared and the logarithmic viscosity was measured, it was found to be 8 r3 dl/ll. The infrared absorption spectrum is shown in Figure/.

Comparison of elemental analysis values with calculated values Calculated values are in repetition units. This is the value calculated based on.

Collect polyimide/I and apply organic solvent 1 with various δ values.
The results of examining the solubility in 001d are shown in Table/.

Table/ Solubility results Next, polyimide powder was mixed with tetrahydrofuran (δ=2.
/) to prepare a 7% by weight solution.

A thin film of this polyimide solution was formed on a glass plate using a doctor knife manufactured by Gardna, and dried in a hot air drying oven at 60° C. for 70 minutes. Next, this semi-dry film was fixed on a metal material and further heated from 120°C to 0°C for 2 years/! The temperature was raised for 2 minutes, and finally heat treated at 300℃ for 2 minutes.
A polyimide film with a diameter of 10 μm was obtained.

The tensile properties of this film are: modulus of elasticity, 22F kg/Ryu2, strength, <kg/H2, elongation! It was 7.7%.

The glass transition temperature is 2 years, 2°C, and the coefficient of thermal expansion is 3x.
10-5/'c, and the thermal decomposition initiation temperature was 90°C.

After coating the tetrahydrofuran solution of polyimide prepared in Example 3 on a copper foil with a thickness of μm for 3 days, the temperature was slowly raised from room temperature to 20°C in a heat dryer and dried to form a polyimide film. Formed. This coating had good gloss and was firmly adhered to the copper foil.

Example 3 In Example/BAPF 10,37 &, 3. ．． 3
'.

Polyimide powder (ηinh /, j dl / ll
) was manufactured.

Dissolve this polyimide powder in tetrano)hydrofuran! A polyimide solution of % by weight was prepared, and a polyimide film was formed on a steel plate in the same manner as in Example. This coating also had good gloss and adhered firmly to the steel plate.

〔Effect of the invention〕

The polyimide resin and composition of the present invention have poor moldability,
It is useful as a coating material and a sleeve material.

[Brief explanation of the drawing]

Figure - / shows the infrared absorption spectrum of the polyimide powder obtained in Example /. Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent attorney For pros and cons - others/famous proceedings] 3 in 1 (voluntary) ■, Indication of case: 1988 Patent Application No. 250916 2, Name of invention: Polyimide resin composition Item 3: Person making the amendment Within Mitsubishi Kasei Corporation 5: Claims column and Detailed Description of the Invention column (2) "Hexachloropropane" on page 17, line 10 of the specification Correct the statement to "hexafluoropropane." Claims (1) General formula (1) % formula % () represents a divalent organic group. A polyimide resin composition obtained by dissolving a polyimide having a repeating unit represented by the following formula in an organic solvent having a solubility coefficient δ ((cal/cm') ``'') in the range of 9 to 14. (2) The polyimide resin composition according to claim 1, wherein the polyimide consists of repeating units represented by (n). (3) The polyimide resin composition according to claim 1, wherein the polyimide consists of repeating units represented by (III). (4) As the organic solvent, at least one solvent selected from the group consisting of "tetrahydrofuran, chloroform, 1,4-dioxane, nitrobenzene" and acetophenone is used. polyimide resin composition.

Claims (4)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R^1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas, chemical formulas, tables, etc. ▼ indicates a tetravalent organic group represented by ▼.
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ indicates a divalent organic group. ) The solubility coefficient δ ([cal/cm^3]^1^/^2) is 9 to 14.
A polyimide resin composition dissolved in an organic solvent in the range of (2) The polyimide resin composition according to claim 1, wherein the polyimide consists of a repeating unit represented by ▲Mathematical formula, chemical formula, table, etc.▼...(II) (3) Polyimide has ▲mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) The polyimide resin composition according to claim 1, characterized in that it consists of repeating units represented by (4) Claims characterized in that at least one solvent selected from the group consisting of tetrahydrofuran, chloroform, 1,4-dioxane, nitrobenzene, diethylene glycol, dimethyl ether, and acetophenone is used as the organic solvent. Polyimide resin composition according to item 1