JPH09263636A - Polyimide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimide resin reduced in cyclic siloxane gas production to a specified level or lower, low in hygroscopicity, excellent in heat resistance and low-temperature processability, and useful as e.g. an electronic material, composed essentially of a specific siliconediamine and an oxydiphthalic dianhydride. SOLUTION: This polyimide resin is composed essentially of a siliconediamine of formula I (R<1> is a divalent hydrocarbon) such as 1,3-bis(3-aminopropyl) tetramethylsiloxane and 4,4'-oxydiphthalic dianhydride, having such a characteristic as to be <0.02wt.%, based on this resin, of the production of a cylic siloxane gas of formula II ((n) is an integer of >=3) when heated at <=350 deg.C for 5min.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyimide resin which is excellent in heat resistance, soluble in an organic solvent and excellent in moldability.

[0002]

2. Description of the Related Art Polyimide resins are widely used as electric and electronic materials because of their high heat resistance, flame retardancy and excellent electrical insulation. It is widely used as a film as a base material for flexible printed wiring boards and heat-resistant adhesive tapes, and as a resin varnish for insulating and protective films of semiconductors.
However, conventional polyimide resins have high hygroscopicity and excellent heat resistance, but on the other hand, they are insoluble and infusible or have extremely high melting points, so that they cannot be said to be easy-to-use materials in terms of workability. It is used as a semiconductor mounting material for interlayer insulating films and surface protection films.For these, a precursor polyamic acid soluble in an organic solvent is applied to the semiconductor surface, and the solvent is removed by heat treatment and imidization is performed. proceeding. At this time, the imidization requires a heating step at a high temperature of 300 ° C. or more for one hour or more, and the device is exposed to a high temperature, thereby lowering the yield of the assembly step. Further, since the film has high hygroscopicity, there is a problem that the absorbed water evaporates at a stretch at a high temperature and causes swelling and cracks.

On the other hand, many thermoplastic polyimide resins and solvent-soluble polyimide resins have been proposed for the purpose of compensating for the drawbacks of these conventional polyimide resins. One of them is a silicone-modified polyimide resin. Silicone-modified polyimide resins are excellent in low hygroscopicity and solvent solubility and are suitable for electronics. However, there is a trade-off between heat resistance, solvent solubility, and low hygroscopicity, which are closely related to the silicone content. The conventional silicone-modified polyimide resin was not sufficient to obtain better reliability.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present invention has been earnestly studied to obtain a polyimide resin having excellent heat resistance, low hygroscopicity, and solubility in an organic solvent and excellent moldability.
The present inventors have found that a polyimide resin having a specific structure can solve the above problems, and arrived at the present invention.

[0005]

[Means for Solving the Problems]

The polyimide resin of the present invention is characterized in that the amount of the cyclic siloxane gas represented by the formula (1) is less than 0.02% by weight of the resin when heated at a temperature not exceeding 350 ° C. for 5 minutes. And a silicone-modified polyimide resin containing silicone diamine represented by the formula (2) and 4,4′-oxydiphthalic dianhydride as essential components.

[0007]

Embedded image (N is an integer of 3 or more)

[0008]

Embedded image (In the formula, R ¹ is a divalent hydrocarbon group)

The polyimide resin of the present invention comprises a mol of the silicone diamine represented by the formula (2), b mol of the silicone diamine represented by the formula (3) and c mol of the other diamine as the amine component, 4,4'-. Oxydiphthalic acid dianhydride (d mol) and another acid dianhydride (e mol) as acid components, and 0.02
≦ a / (a + b + c) ≦ 0.50 and b / (a + b +
c) ≤ 0.02 and 0.6 ≤ d / (d + e) and 0.9
A polyimide resin soluble in an organic solvent, which is obtained by reacting both components at a molar ratio of 6 ≦ (d + e) / (a + b + c) ≦ 1.04 and is imide-cyclized, or the molecular end of the polyimide resin is represented by the general formula (5). Endcapping with f mole of acid anhydride of 0.02 ≦ a / (a + b + c) ≦ 0.50 and b / (a + b + c) ≦ 0.02 and 0.6 ≦ d / (d
+ E + 0.5f) and 0.002 ≦ 0.5f / (d + e
+ 0.5f) ≦ 0.05 and 0.96 ≦ (d + e + 0.
5f) / (a + b + c) ≦ 1.04 molar ratio of both components are reacted to imide ring-close the polyimide resin soluble in an organic solvent or the aromatic polymer represented by the general formula (6) at the molecular end of the polyimide resin. Endcapped with g mol of amine and 0.02 ≦ a / (a + b + c + 0.5 g) ≦
0.50 and b / (a + b + c + 0.5g) ≦ 0.02
And 0.002 ≦ 0.5g / (a + b + c + 0.5g)
≦ 0.05 and 0.6 ≦ d / (d + e) and 0.96 ≦
It is a polyimide resin soluble in an organic solvent in which both components are reacted at a molar ratio of (d + e) / (a + b + c + 0.5 g) ≦ 1.04 to cause imide ring closure.

[0010]

Embedded image (In the formula, R ² is a divalent hydrocarbon group, n is an integer of 2 to 20)

[0011]

Embedded image

[0012]

Embedded image

[0013]

[Chemical 6] (Wherein Y is a hydrogen atom or at least one group selected from methyl, ethyl, propyl, butyl, phenyl, methoxy, ethoxy, propoxy, butoxy or phenoxy groups).

The silicone diamine represented by the formula (2) used in the present invention is 1,3-bis (3-aminopropyl) tetramethylsiloxane and has a low water absorption property.
Used to impart low temperature processability and solubility in solvents.
Further, these short-chain silicone diamines are excellent in heat resistance and can produce a resin having higher reliability at high temperatures than using other silicone diamines. It is preferable to use the silicone diamine in the range of 2 to 50 mol% of the total amine component. If it is less than 2 mol%, low hygroscopicity, low temperature processability and solubility in a solvent will not be exhibited, and if it exceeds 50 mol%. The glass transition temperature is remarkably lowered, causing a problem in heat resistance. A more preferable amount of addition is 10 mol% to 35 mol% of all amine components from the viewpoint of low hygroscopicity, low-temperature processability, solubility in a solvent, and heat resistance.

The silicone diamine represented by the formula (3) used in the present invention is α, ω-bis (3-aminopropyl) polydimethylsiloxane and the like, and when used in combination with the one represented by the formula (2), low water absorption is obtained. Properties, low-temperature processability, and solubility in solvents are significantly improved. Particularly, the range of n of 4 to 13 is preferable from the viewpoint of glass transition temperature and workability. However, since this silicone diamine decomposes at high temperature to generate the cyclic siloxane gas represented by the formula (1), it may cause foaming of the resin and contamination of surrounding materials. It should be 2 mol% or less of the amine component. The more preferable addition amount is 0.2 to 0.2% of all amine components in view of low hygroscopicity, low temperature processability, and heat resistance at high temperature.
It is 0.8 mol%.

4,4'- which is the main constituent of the acid component
The amount ratio of oxydiphthalic dianhydride is extremely important for the solubility of the obtained polyimide resin, and if it is not within the above range, the feature of the present invention that it is dissolved in a low boiling point solvent is lost.

Other diamines used in the present invention include 2,2-bis (4- (4-aminophenoxy) phenyl) propane and 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane. 2,2-bis (4-aminophenoxy) hexafluoropropane,
Bis-4- (4-aminophenoxy) phenylsulfone, bis-4- (3-aminophenoxy) phenylsulfone, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene,
1,4-bis (4-aminophenoxy) benzene, 1,
4-bis (3-aminophenoxy) benzene, 4,4 ′
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone,
One or two kinds of 4,4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl and the like can be used in combination. Above all, it is preferable to use a diamine having an aminophenoxy structure in an application field in which adhesiveness is important.

Other acid dianhydrides used in the present invention include 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride and 3,3', 4,4'-biphenyl tetracarboxylic dianhydride. It is possible to use one kind or a combination of two kinds of anhydrides, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride and the like.

The diamine represented by the formula (4) includes 1,3-bis (3-aminophenoxy) benzene and 1,4-bis (4-aminophenoxy) benzene, and particularly 1,3-bis (3 The use of -aminophenoxy) benzene is preferable from the viewpoint of solubility in low boiling point solvents and low temperature processability.

When the polyimide is used for an adhesive or a molding material, the end of the molecule is end-capped to control the molecular weight, whereby a melt viscosity suitable for adhesion and molding can be obtained and processability can be improved. it can. The amount ratio of the acid anhydride or the aromatic amine as the end cap agent is preferably within the above range. If the amount is less than this range, the molecular weight becomes too high, and the solubility in a low boiling point solvent, which is a feature of the present invention, decreases, and in applications where importance is placed on adhesiveness, wettability decreases due to an increase in melt viscosity, which is not preferable. On the other hand, if the amount is above this range, the molecular weight will be remarkably reduced, causing a problem in heat resistance. From the viewpoints of low-temperature processability, heat resistance, and mechanical strength, the endcapping agent is more preferably in the range of 0.4 to 2.4 mol% of the total acid component or the total amine component.

Examples of the end cap agent include the acid anhydride represented by the general formula (5) and the aromatic amine represented by the general formula (6). As the acid anhydride, phthalic anhydride, maleic anhydride, nadic acid anhydride and the like are used, and as the aromatic amine, p-methylaniline, p-methoxyaniline, p-phenoxyaniline and the like are used.

The equivalence ratio between the acidic component and the amine component in the polymerization reaction is an important factor that determines the molecular weight of the polyamic acid obtained. It is well known that there is a correlation between the molecular weight and physical properties of polymers, especially the number average molecular weight and mechanical properties. The larger the number average molecular weight, the better the mechanical properties. Therefore, in order to obtain practically excellent strength, it is necessary to have a high molecular weight to some extent. In the present invention, the equivalent ratio r of the acidic component and the amine component is preferably 0.96 ≦ r ≦ 1.04. 0.98 ≦ r ≦ 1.0
The range of 2 is more preferable from the viewpoint of both mechanical strength and heat resistance.

The reaction between the tetracarboxylic dianhydride and the diamine is carried out by a known method in an aprotic polar solvent. Aprotic polar solvents include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (D
MAC), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), diglyme, cyclohexanone, 1,4-dioxane (1,4-DO) and the like. The aprotic polar solvent may be used alone or in combination of two or more. At this time, a non-polar solvent compatible with the aprotic polar solvent may be mixed and used. Aromatic hydrocarbons such as toluene, xylene and solvent naphtha are often used. The proportion of the nonpolar solvent in the mixed solvent is preferably 30% by weight or less. This is because if the nonpolar solvent is 30% by weight or more, the solvent power of the solvent may be reduced and polyamic acid may be precipitated. The reaction between the tetracarboxylic dianhydride and the diamine is carried out by dissolving the well-dried diamine component in the above-mentioned reaction solvent that has been dehydrated and purified, and adding thereto the ring-closing rate of 98%, more preferably 99% or more. The reaction is allowed to proceed by adding the anhydride.

The polyamic acid solution thus obtained is subsequently heated to dehydration and cyclization in an organic solvent to give an imidized polyimide. Since the water generated by the imidization reaction interferes with the ring-closing reaction, an organic solvent that is not compatible with water is added to the system to azeotropically evaporate it and use a device such as a Dean-Stark tube to remove it from the system. To discharge. Dichlorobenzene is known as an organic solvent that is incompatible with water,
For electronics use, the above-mentioned aromatic hydrocarbons are preferably used because chlorine components may be mixed therein.
Further, it does not prevent the use of compounds such as acetic anhydride, β-picoline, and pyridine as a catalyst for the imidization reaction.

In the present invention, the higher the degree of imide ring closure, the better, and if the imidization ratio is low, imidization occurs due to heat during use and water is not generated, which is not preferable. Therefore, 95% or more, more preferably 98% or more. It is desirable that the imidization ratio of is achieved.

The method and use of the polyimide resin of the present invention are not particularly limited, but the resin varnish can be used as it is for coating or dipping, or the varnish can be cast and dried to form a film. . It is also possible to use it as a solid resin for extrusion molding. Examples of a method for solidifying the solid include reprecipitation in a poor solvent. Even when used as a resin varnish, particularly when used for electronic applications that dislike impurities and foreign substances, it is preferable to use a resin that has been reprecipitated and solidified once again dissolved in an organic solvent and filtered.

The polyimide resin of the present invention is an almost completely imidized polyimide resin having a specific structure which is soluble in an organic solvent. By limiting the chain length and the amount ratio of the silicone diamine, which is the raw material of the polyimide, it is possible to achieve heat resistance far exceeding that of conventional silicone-modified polyimide while maintaining low hygroscopicity and low-temperature processability. Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

[0028]

【Example】

(Example 1) NMP384 dehydrated and refined in a four-necked flask equipped with a dry nitrogen gas inlet tube, a condenser, a thermometer, and a stirrer.
g, and stir vigorously for 10 minutes while flowing nitrogen gas. Next, 2,2-bis (4- (4-aminophenoxy) phenyl) propane 30.665 g (0.075 mol) and 1,3-bis (3-aminophenoxy) benzene 21.838 g (0.075 mol) And 1,3-bis (aminopropyl) tetramethylsiloxane 9.050g
(0.036 mol) and 0.782 g (average molecular weight 837, 0.001 mol) of α, ω-bis (3-aminopropyl) polydimethylsiloxane are charged, and the system is heated to 60 ° C and stirred until uniform. . After being uniformly dissolved, the system was cooled to 5 ° C. in an ice water bath, and 45.884 g (0.149 mol) of 4,4′-oxydiphthalic acid dianhydride and 3,3 ′, 4,4.
4'-benzophenone tetracarboxylic dianhydride 11.
915 g (0.037 mol) was added as a powder over 10 minutes, and then stirring was continued for 5 hours to obtain a polyamic acid solution. During this time, the flask was kept at 5 ° C.

Thereafter, the nitrogen gas introducing pipe and the cooler were removed,
A Dean Stark tube filled with xylene was attached to the flask and xylene was added to the system. The ice water bath was replaced with an oil bath to heat the system and remove the generated water outside the system. After heating for 4 hours, no water was generated from the system.
After cooling, the reaction solution was poured into a large amount of methanol to precipitate a polyimide resin. After filtering the solids,
Drying under reduced pressure for 2 hours gave a solid resin. When the infrared absorption spectrum was measured by the KBr tablet method, an absorption of 5.60 μm derived from a cyclic imide bond was observed, but an absorption of 6.06 μm derived from an amide bond could not be observed, and this resin was almost 100%. It was confirmed that the film was% imidized.
The gas generated when the polyimide resin was heated was measured by the purge-and-trap GC-MS method.
The total amount of the cyclic siloxane represented by the formula (1) generated by heating for 1 minute was 0.0012% by weight of the resin.

The above polyimide resin was dissolved in cyclohexanone to obtain a polyimide resin varnish having a solid content of 25%. This varnish was coated with a reverse roll coater on a biaxially stretched polyester film (trade name: Diafoil, thickness: 50μ).
m, manufactured by Mitsubishi Rayon Co., Ltd.), dried and peeled from the biaxially stretched polyester film to obtain a uniform film having a thickness of 30 μm without a support. Maximum drying temperature is 1
The drying time was 6 minutes at 80 ° C. Peeling was easy and there was no particular problem. A test piece was prepared by thermocompression-bonding this film to a stainless steel plate (heat-compression-bonding at 300 ° C. for 2 seconds, releasing the pressure and annealing at 300 ° C. for 30 seconds. The pressure applied to the adhesive surface was calculated from the gauge pressure and the adhesive area. Result 4kgf / cm
^{Was 2} . ), The 180 degree peel strength of this test piece was 2.0 kgf / cm, and showed an excellent adhesive force. In addition, the contact angle of pure water to the stainless steel surface near the tape attachment part was measured before and after attachment to check the presence or absence of contamination by decomposed gas from the tape during attachment, but no change was observed at 60 ° before and after attachment. It was

(Examples 2 to 6) In the same manner as in Example 1, polyimide resin and its organic solvent solution and film were prepared with the formulations shown in Table 1, and the same evaluations as in Example 1 were performed. Shown in 1.

[0032]

[Table 1]

In Table 2, ODPA is 4,4'-oxydiphthalic dianhydride and BTDA is 3,3 ', 4,4'.
-Benzophenone tetracarboxylic dianhydride, PA is phthalic anhydride, BAPP is 2,2-bis (4- (4-
Aminophenoxy) phenyl) propane, APB is 1,3-bis (3-aminophenoxy) benzene, A
PDS is an abbreviation for 1,3-bis (aminopropyl) tetramethylsiloxane, APPS is an abbreviation for α, ω-bis (3-aminopropyl) polydimethylsiloxane, and PPA is an abbreviation for p-phenoxyaniline.

(Comparative Examples 1 to 5) In the same manner as in Example 1, preparation of a polyimide resin, an organic solvent solution thereof and a film was attempted with the formulations shown in Table 2. Table 2 shows the obtained evaluation results.

[0035]

[Table 2]

The above examples show that the present invention makes it possible to obtain a polyimide resin which is soluble in an organic solvent and has both low-temperature processability and high-temperature heat resistance.

[0037]

According to the present invention, it is possible to provide a polyimide resin having both heat resistance and low temperature processability. Since it is soluble in a low boiling point solvent, the residual solvent can be almost completely eliminated, and since it has already been imidized, a high-temperature process for imidization is unnecessary during processing, and no water is generated. For this reason, it is extremely useful industrially as a material for electronics requiring high reliability and heat resistance.

Claims (7)

[Claims] 1. The amount of cyclic siloxane gas represented by the formula (1) generated when heated for 5 minutes at a temperature not exceeding 350 ° C. is less than 0.02% by weight of the resin, and the formula (1) Silicone diamine represented by 2) and 4,4'-
Silicone-modified polyimide resin containing oxydiphthalic dianhydride as an essential component. Embedded image (N is an integer of 3 or more) (In the formula, R ¹ is a divalent hydrocarbon group) 2. An amine component comprising a mol of the silicone diamine represented by the formula (2), b mol of the silicone diamine represented by the formula (3) and c mol of the other diamine, 4,4′-oxydiphthalic acid dianhydride. d mol and another mol of acid dianhydride as an acid component, and 0.02 ≦ a / (a + b + c) ≦
0.50 and b / (a + b + c) ≦ 0.02 and 0.6
≤d / (d + e) and 0.96≤ (d + e) / (a + b
The polyimide resin according to claim 1, which is soluble in an organic solvent in which both components are reacted at a molar ratio of + c) ≦ 1.04 to cause imide ring closure. Embedded image (In the formula, R ² is a divalent hydrocarbon group, n is an integer of 2 to 20) 3. An amine component, 4,4 ′, wherein a mole of the silicone diamine represented by the formula (2), b mole of the silicone diamine represented by the formula (3) and c mole of the diamine represented by the formula (4) are used. -Using d mol of oxydiphthalic dianhydride as an acid component and 0.02≤a / (a + b + c) ≤0.50
And b / (a + b + c) ≦ 0.02 and 0.5 ≦ c /
(A + b + c) and 0.96 ≦ d / (a + b + c) ≦
The polyimide resin according to claim 1, which is soluble in an organic solvent in which both components are reacted at a molar ratio of 1.04 to cause imide ring closure. Embedded image 4. A mole of the silicone diamine represented by the formula (2), b mole of the silicone diamine represented by the formula (3) and c mole of the other diamine as an amine component, 4,4′-oxydiphthalic acid dianhydride. d mol and another e dianhydride acid are used as acid components, and the molecular end of the polyimide resin is end-capped with f mol of the acid anhydride represented by the general formula (5).
And 0.02 ≦ a / (a + b + c) ≦ 0.50 and b /
(A + b + c) ≦ 0.02 and 0.6 ≦ d / (d + e +
0.5f) and 0.002 ≦ 0.5f / (d + e + 0.
5f) ≦ 0.05 and 0.96 ≦ (d + e + 0.5f)
The polyimide resin according to claim 1, which is soluble in an organic solvent in which both components are reacted at a molar ratio of /(a+b+c)≦1.04 and imide ring-closed. Embedded image 5. A mole of the silicone diamine represented by the formula (2), b mole of the silicone diamine represented by the formula (3) and c mole of the other diamine are used as an amine component and 4,4′-oxydiphthalic dianhydride. d mol and another mol of acid dianhydride as an acid component, the molecular end of the polyimide resin is end-capped with g mol of the aromatic amine represented by the general formula (6), and 0.02 ≦ a / ( a + b + c + 0.5g) ≦
0.50 and b / (a + b + c + 0.5g) ≦ 0.02
And 0.002 ≦ 0.5g / (a + b + c + 0.5g)
≦ 0.05 and 0.6 ≦ d / (d + e) and 0.96 ≦
The polyimide resin according to claim 1, which is soluble in an organic solvent in which both components are reacted at a molar ratio of (d + e) / (a + b + c + 0.5 g) ≦ 1.04 to cause imide ring closure. [Chemical 6] (Wherein Y is a hydrogen atom or at least one group selected from methyl, ethyl, propyl, butyl, phenyl, methoxy, ethoxy, propoxy, butoxy or phenoxy groups). 6. An amine component containing 4,4 ′ of a silicone diamine represented by the formula (2), b mole of the silicone diamine represented by the formula (3) and c mole of the diamine represented by the formula (4). -Using d mol of oxydiphthalic dianhydride as an acid component, end-capping the molecular end of the polyimide resin with f mol of the acid anhydride represented by the general formula (5), and
02 ≦ a / (a + b + c) ≦ 0.50 and b / (a + b
+ C) ≦ 0.02 and 0.5 ≦ c / (a + b + c) and 0.002 ≦ 0.5f / (d + 0.5f) ≦ 0.05 and 0.96 ≦ (d + 0.5f) / (a + b + c) ≦ 1 ．
The polyimide resin according to claim 1, which is soluble in an organic solvent in which both components are reacted at a molar ratio of 04 to cause imide ring closure. 7. An amine component, 4,4 ′, wherein a mole of the silicone diamine represented by the formula (2), b mole of the silicone diamine represented by the formula (3) and c mole of the diamine represented by the formula (4) are used. -Using d mol of oxydiphthalic acid dianhydride as an acid component, end-capping the molecular end of the polyimide resin with g mol of the aromatic amine represented by the general formula (6), and 0.02≤a / (a + b + c + 0.5 g ) ≦ 0.50 and b / (a + b + c + 0.5g) ≦ 0.02 and 0.5
≤c / (a + b + c + 0.5g) and 0.002≤0.
5g / (a + b + c + 0.5g) ≦ 0.05 and 0.9
The polyimide resin according to claim 1, which is soluble in an organic solvent in which both components are reacted at a molar ratio of 6 ≦ d / (a + b + c + 0.5 g) ≦ 1.04 to cause imide ring closure.