JP3446560B2 - Block polyimide resin and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive block polyimide resin and a method for manufacturing the same, and more particularly to a new type block polyimide resin that can be used as a material for electronic devices and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, polyimide resins have excellent heat resistance, electrical insulation, and abrasion resistance, and further have appropriate mechanical strength and mechanical elongation, so that they are flexible printed. Widely used in heat-resistant insulating coating materials for electronic and electric parts such as films for substrates, aerospace fields, vehicles and the like. Further, in the homopolymer in which the component of the polyimide resin is composed of one type of acid component and one type of diamine component,
Since it is difficult to give a special function, a multi-component polyimide resin has been conventionally developed.

Generally, as a conventional method for producing a polyimide resin, first, an equal molar amount of a high-purity acid dianhydride and an aromatic diamine are mixed, and a polycondensation reaction is carried out in a polar solvent at a low temperature. , To produce high molecular weight polyamic acid. Next, a solution of this polyamic acid is cast-formed, and a dehydration ring closure reaction is carried out by heating or chemical treatment by addition of acetic anhydride to produce a stable polyimide resin.

In this conventional method, the polyamic acid produced as an intermediate is unstable to heat and easily produces water to imidize when heated. The produced water acts on the polyamic acid to promote the hydrolysis of the polyamic acid and breaks the molecular chain, so that the produced polyamic acid becomes a low molecular weight polyamic acid. Therefore, by keeping the production temperature of polyamic acid at a low temperature below room temperature,
It produces high molecular weight polyamic acid.

Generally, high molecular weight polyamic acid is N-
Although it is soluble in polar solvents such as methylpyrrolidone (NMP) and dimethylboramide (DMF), high molecular weight polyimide resins are insoluble in most solvents.
In the production of the polyimide resin, a two-step synthetic method of producing the polyimide resin via polyamic acid is adopted.

Polyimide resins are insoluble in solvents and have problems in storage stability and processability. Further, in the case of random copolymers, the characteristics are inferior to those of each constituent component of the copolymer. Conventionally, a polyimide resin has been manufactured by a block copolymerization method.

JP-A-60-166326 describes a block-type polyimide resin produced by producing a sulfonamide oligomer and adding an acid dianhydride thereto.

Japanese Unexamined Patent Publication No. 64-1683 and Japanese Unexamined Patent Publication No.
In JP-A-21165, a copolymer polyimide resin produced by a sequential addition method is described. This polyimide resin is first reacted with an aromatic diamine by adding too much or too little acid dianhydride to produce a polyamic acid prepolymer, and then adding a shortage of diamine to this polyamic acid prepolymer. It is produced by producing a polyamic acid copolymer and subjecting it to chemical treatment or heat treatment.

Further, Japanese Patent Application Laid-Open No. 1-211165 discloses that
Films of polyimide resin are described. This film is prepared by first adding 1.5 to 2.0 mol% of an acid dianhydride to a diamine in a polar solvent and reacting at a low temperature to synthesize an oligomer of amic acid. It is prepared by adding an equal amount of isocyanate and reacting to generate a polyimide amide carboxylic acid while generating carbon dioxide gas, casting the polyimide amide carboxylic acid and heating.

The above-mentioned JP-A-60-166326, JP-A-64-1683, and JP-A-1-21165.
Since the polyimide resin of the publication is a block copolymer in its constitution, it is excellent in mechanical strength, heat resistance, heat aging resistance and workability.

Further, Japanese Patent Laid-Open No. 2-91124 discloses that
Polysiloxane resins of siloxane-imide block copolymers are described. The siloxane-imide block copolymer polyimide resin is prepared by first adding an acid dianhydride to a diaminosiloxane copolymer to form a siloxane-amic acid block copolymer, and then forming the siloxane-amic acid copolymer. It is manufactured by adding an equal amount of diamine to a block copolymer to form a polyamic acid, which is then chemically treated or heat-treated.

The polyimide resin disclosed in JP-A-2-91124 has excellent adhesion to the substrate.

[0013]

However, since the conventional polyimide resin as described above is produced by the two-step polymerization shrinkage method via the polyamic acid, the produced high molecular weight polyamic acid is not heated. Is unstable to
Water generated by heat promotes hydrolysis to break the molecular chain, and recondenses at the imidization stage to exhibit random copolymerizability, resulting in inferior properties to those of each component. was there.

The high molecular weight polyamic acid, which is an intermediate, can exchange the acid amide groups easily and quickly between the molecules, so that the polyamic acid produced even when two different block polymers are linked together. However, there is a problem that the block polyimide resin containing ionic impurities such as sodium ions and chlorine ions and having randomness cannot be prevented and the original function cannot be exhibited.

Further, according to the conventional polyimide resin, there is a problem that peeling or cracking of parts occurs when it is used in electronic parts because the adhesive effect is lowered due to moisture absorption.

Accordingly, an object of the present invention is to provide a multi-component system having a small amount of ionic impurities, high adhesiveness, low water absorption, which is different from the conventional random copolymerized polyimide resin and block copolymerized polyimide resin. To provide a block polyimide resin and a method for producing the same.

[0017]

In order to achieve the above-mentioned objects, the present invention provides:

[Chemical 1]

[Chemical 2] as well as

[Chemical 3] Three kinds of aromatic diamines represented by

[Chemical 4] as well as

[Chemical 5] A block polyimide resin comprising two kinds of acid dianhydrides represented by and silicone diamine.

In order to achieve the above object, in a polar solvent heated in the presence of a lactone catalyst.

[Chemical 6] And an aromatic diamine represented by

[Chemical 7] By reacting an acid dianhydride represented by

[Chemical 8] as well as

[Chemical 9] And an aromatic diamine represented by

[Chemical 10] Add an acid dianhydride represented by
Direct imidization can be achieved by sequential addition reactions that cause additional reactions.
And a method for manufacturing a block polyimide resin.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Aromatic diamines suitable for achieving the object of the present invention include:

[Chemical 11] 3,4 diaminodiphenyl ether represented by (hereinafter referred to as "DADE"),

[Chemical 12] 2,2-bis [4- (4-aminophenoxy) phenyl] propane represented by (hereinafter referred to as "BAPP"),

[Chemical 13] Examples thereof include bis [4- (3-aminophenoxy) phenyl] sulfone (hereinafter referred to as “BAPS”) represented by the formula (1), benzenediamine, 1,3benzenediamine, 6- Methyl 1,3-benzenediamine, 4,4'-diamino-3,3'-dimethyl-1.1'-biphenyl, 4,4'-methylenebis (benzeneamine), 4,4'-oxybis (benzeneamine) , 3,3'-carbonyl (benzenamine),
4,4'-thiobis (benzeneamine), 4,4'-sulfonyl (benzeneamine), 4,4'-diaminobenzanilide, 2,6-diaminopyridine, 4,4'-diamino-3,3 ', 5,5'-tetramethylbiphenyl, 1,4-bis (4-aminophenoxy) benzene,
4,4'-diaminobenzanilide and the like can also be used.

Suitable acid dianhydrides for achieving the object of the present invention include:

[Chemical 14] Bicyclo (2,2,2) oct-7-ethene-2,3,5,6 tetracarboxylic dianhydride represented by
"CD"),

[Chemical 15] Examples thereof include 3,4,3,4-biphenyltetracarboxylic acid dianhydride (hereinafter referred to as "BPDA"), and benzophenone tetracarboxylic acid dianhydride and bis (dicarboxyl). Phenyl) propane dianhydride, bis (dicarboxyphenyl) sulfone dianhydride, bis (dicarboxyphenyl) ether dianhydride, thiophenetetracarboxylic dianhydride, pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride , 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride and the like can also be used.

In the present invention, by introducing a silicone-based diamine into the polymer main chain in addition to the diamine component and the acid dianhydride, the adhesiveness is excellent and the water absorption is 1.0%.
The following cured product is obtained. As a cause of peeling, cracks, and the like in the field of electronic components, moisture absorption of an adhesive (cured product) is considered, but the inventors have found that the hygroscopicity is improved by introducing a silicone-based diamine. The content of the silicone-based diamine is preferably 1 to 20 mol%. If it is too small, the effect of improving the hygroscopicity is small, and if it is too large, the heat resistance, which is a characteristic of the block polyimide resin, tends to be impaired. Diaminosilane can be given as a representative example of the silicone-based diamine.

As the lactone catalyst, γ-valerolacurone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, γ-tetronic acid, γ-phthalide,
Lactones such as γ-phthalide and pyridine, quinoline, N
A mixture with a base such as methylmorpholine. The mixing ratio is preferably 1/1 to 1/3 in terms of molecular weight ratio. The amount of the lactone catalyst used is 1/4 to 1/200 mol, preferably 1/4 to 1/10 with respect to the acid dianhydride.
It is 0 mol.

As the polar solvent, N-methyl-2-pyrrolidone (hereinafter referred to as "NMP"), dimethylformamide, dimethylacetamide, sulfolane, anisole,
Examples thereof include dioxolane, dioxane and butyrolactone, and two or more kinds of these may be mixed and used.

The reaction temperature is 120 ° C. or higher, preferably 1
It is 40 to 200 ° C. The higher the reaction temperature, the shorter the time required for condensation, but if the temperature is higher, the side reaction is generated with the decomposition of the solvent and the aromatic diamine. The polymerization is performed in an atmosphere of an inert gas such as nitrogen, argon or helium.

In the present invention, since water is produced by the condensation reaction, when water is removed out of the system by azeotropy by adding toluene, xylene, tetralin, etc., the imidization reaction is promoted and a high molecular weight polyimide is obtained. A resin can be obtained.

In the present invention, aromatic diamine and acid dianhydride are reacted in a polar solvent heated in the presence of a lactone catalyst, and aromatic diamine, acid dianhydride and silicone diamine are added successively. The reaction method directly produces a block polyimide resin of four-component system or more,
Random copolymerization due to conversion reaction between amic acids can be prevented, the original characteristics of each component can be sufficiently exhibited, and a desired resin suitable for various applications can be obtained. For example,
By replacing the polymer component having insufficient mechanical strength with another polymer component or adding another polymer component,
The mechanical strength can be supplemented without impairing other properties. In addition, it contains a small amount of ionic impurities such as chlorine ions and sodium ions, and is suitable for use in electronic devices. Furthermore, since the reaction liquid can be used as it is as a varnish, it can be adjusted so that a desired solid content can be obtained in the raw material charging step.
The film thickness can be freely adjusted, and in the field of electronic components such as semiconductors, for example, the varnish coating thickness between the substrate and the chip can be increased, and problems such as chip taps can be avoided.

In the present invention, the weight molecular weight (in terms of polystyrene) of the block polyimide resin is preferably 20,000 or more from the viewpoint of heat resistance and film forming property, and 100,000 or less from the viewpoint of adhesiveness and gelation prevention. . A preferred molecular weight range is 40,000-80,000.

Further, the solid content of the polyimide resin solution is preferably in the range of 20 to 40% by weight, and if it is less than 20% by weight, it is difficult to make the coating film thick and 40% by weight.
If it exceeds, the viscosity of the varnish becomes high and the coating property becomes poor.

[0029]

EXAMPLES The block polyimide resin of the present invention and the method for producing the same will now be described in detail with reference to some examples. <Example 1> A stirrer and a ball cooling tube are attached to a 1000 ml separable three-necked flask for producing a block polyimide resin. This ball-equipped cooling pipe is equipped with a trap with a silicone cock.

Into this three neck flask was added 9.93 g of bicyclo (2,2,2) oct-7-ene-2,3,5,6.
Tetracarboxylic acid dianhydride (BCD), 12.01 g of 3,4 diaminodiphenyl ether (DADE), 1.
5 g γ-valerolactone, 2.4 g pyridine, 20
Add 0 g of NMP and 30 g of toluene, and stir with a stirrer for 10 minutes in a nitrogen atmosphere at room temperature. After that, the temperature is raised to 180 ° C. and the rotation speed of the stirrer is changed to 180 r.
Stir for 1 hour at pm.

Next, this reaction solution was cooled by air and cooled to 32.365.
g of 3,4,3,4-biphenyltetracarboxylic dianhydride (BPDA), 8.2 g of diaminosilane (manufactured by Shin-Etsu Chemical: X-22-161AS), 17.3 g of bis [4
-(3-Aminophenoxine) phenyl] sulfone (B
APS), 16.4 g of bis [4- (4-aminophenoxine) phenyl] propane (BAPP), 163 g of NMP, and 30 g of toluene were added, and 180 ° C. was added again.
The temperature is raised to 1, and the reaction is carried out by stirring with a stirrer for 5 hours to form a reaction liquid (varnish). At this time, the rotation speed of the stirrer is initially set to 180 rpm and is lowered as the reaction proceeds. Further, the water produced during the reaction is removed from the silicon cock.

A part of this varnish is poured into an excess of methanol and stirred with a mixer to precipitate a block polyimide resin, which is dried to form a powder. The powder is washed with methanol, dried at room temperature, and then dried under reduced pressure at 150 ° C. to produce powder. When the infrared absorption spectrum of this powder was measured, it was 720 cm-1, 1365 cm-
The characteristic absorption of imide was observed at 1, 1721 cm -1, and 1780 cm -1.

A part of the varnish is cast on a glass substrate as it is, dried at 150 ° C., peeled off from the glass substrate, and heat-treated at 250 ° C. to obtain a film that is tougher than the conventional one. Was able to create. Moreover, when the molecular weight of the varnish was examined using gel permeation chromatography (GPC), Mw = 63500
Met.

<Embodiment 2> 1000 m as in Embodiment 1.
In a 1-liter separable 3-neck flask, 9.93 g of BC
D, 12.01 g of DADE, 1.5 g of γ-valerolactone, 2.4 g of pyridine, 200 g of NMP, and 30 g of toluene were added, and the mixture was stirred with a stirrer for 10 minutes in a nitrogen atmosphere at room temperature. After that, the temperature is raised to 180 ° C., the rotation speed of the stirrer is set to 180 rpm, and the mixture is stirred for 1 hour.

Next, the reaction solution was air-cooled to obtain 35.31 g.
BPDA, 16.4 g of diaminosilane (X-22-161AS manufactured by Shin-Etsu Chemical), 17.3 g of BAPS,
16.4 g BAPP, 207 g NMP, and 30 g
Toluene was added, the temperature was raised to 180 ° C. again, and the mixture was stirred and reacted for 5 hours with a stirrer to form a varnish. At this time, the rotation speed of the stirrer is initially set to 180 rpm,
Decrease as the reaction proceeds. Further, the water produced during the reaction is removed from the silicon cock.

A part of this varnish was cast on a glass substrate as it was, dried at 150 ° C., peeled off from the glass substrate and heat-treated at 250 ° C. to obtain a film tougher than the conventional one. I was able to create it. Moreover, when the molecular weight of the varnish was examined using GPC, it was Mw (polystyrene conversion) = 62800.
Furthermore, the varnish was heated at 250 ° C. for 2 hours, and the solid content thereof was examined and found to be 20.3%.

<Comparative Example 1> 1000 m as in Example 1
In a 1-liter separable 3-neck flask, 9.93 g of BC
D, 12.01 g of DADE, 1.5 g of γ-valerolactone, 2.4 g of pyridine, 200 g of NMP, and 30 g of toluene were added, and the mixture was stirred with a stirrer for 10 minutes in a nitrogen atmosphere at room temperature. After that, the temperature is raised to 180 ° C., the rotation speed of the stirrer is set to 180 rpm, and the mixture is stirred for 1 hour.

Next, the reaction solution was air-cooled to give 29.43 g.
BPDA, 17.3 g BAPS, 16.4 g BA
PP, 140 g of NMP, and 30 g of toluene were added, the temperature was raised to 180 ° C. again, and the mixture was stirred and reacted for 5 hours with a stirrer to form a varnish. At this time, the rotation speed of the stirrer is initially set to 180 rpm and is lowered as the reaction proceeds. Further, the water produced during the reaction is removed from the silicon cock.

A part of this varnish was cast on a glass substrate as it was, dried at 150 ° C., peeled off from the glass substrate and heat-treated at 250 ° C. to form a film. Moreover, when the molecular weight of the varnish was examined using GPC, it was Mw (polystyrene conversion) = 62000. Furthermore, the varnish was heated at 250 ° C. for 2 hours, and the solid content thereof was examined and found to be 20.3%.

<Comparative Example 2> Rica coat PN20, which is a ready-made varnish manufactured by Shin Nippon Rika Co., Ltd., was cast on a glass substrate, dried at 150 ° C., peeled off from the glass substrate, and heat-treated at 250 ° C. Make a film.

The results of measuring the properties of the block polyimide resins produced in the examples and comparative examples are shown in Table 1.

[0042]

[Table 1]

The evaluation of various characteristics shown in Table 1 is based on the following methods.

Glass transition point: Seiko Electronic Industry Co., Ltd.
The glass transition point was measured from room temperature to 300 ° C. at a temperature rising rate of 10 ° C./min by using a thermo-mechanical analyzer TMA120 manufactured by K.K.

1% thermogravimetric reduction temperature: differential thermogravimetric simultaneous measurement apparatus TG / DTA32 manufactured by Seiko Instruments Inc.
0 at room temperature to 700 ° C at a flow rate of 100 ml / min in nitrogen or air at a temperature rising rate of 10 ° C / min.
Thermal analysis was performed until the temperature at which the weight was reduced by 1% was determined.

Thermal expansion coefficient: manufactured by Seiko Electronics Co., Ltd.
4x20mm using thermomechanical analyzer TMA120
Using a quartz probe for tension, the film cut to length is
Tensile temperature 5 ~ 3, room temperature to 3 at a heating rate of 10 ° C / min
The measurement was performed up to a temperature range of 00 ° C.

Volume resistivity: A sample was set in a specific resistance cell made by Hewlett Packard, and a high insulation resistance meter 329A made by Yokogawa Hewlett Packard was used, and DC 100V / 1.
It was calculated from the current value after the voltage application. The temperature is 21 ℃
It was performed at ± 2 ° C. and a humidity of 60 ± 5%.

Ionic impurities: The film was cut into 50 × 100 mm pieces and 100 ml containing 50 ml of ultrapure water.
Dip the film in a stainless beaker and dry in a dryer for 10
Heat extraction was performed at 0 ° C./0.5 hours. This extract was applied to Na ⁻ , Cl ⁺ , NO using an ion chromatograph analyzer IC7000 manufactured by Yokogawa Analytical Systems Co., Ltd.
Quantitative analysis was carried out for ₃ ^- and SO ₄ ^2- .

Water absorption rate: 100 × 100 m of the produced film
The test pieces are cut into m pieces and placed in a dryer at 150 ° C. ± 3 ° C. and dried for 30 minutes. Then, after cooling to room temperature in a desiccator, it is placed in a weighing bottle, tightly closed, and the weight in a dry state is measured (W1). Next, soak the test piece in pure water at 23 ° C for 24 hours,
Within 1 minute after taking out, the adhered water is quickly wiped off with a bencot, put in a weighing bottle and tightly stoppered, and the weight after water absorption is measured (W2). The water absorption was calculated according to the following formula, and the average of two points was used as the result. Water absorption rate = (W2-W1) x 100 / W1

Storage elastic modulus: 25 × 4 mm for the prepared film
Cut to size and use a dynamic viscoelasticity measuring device DVA-200 manufactured by IT Measurement Control Co., Ltd., with a frequency of 10 Hz,
The temperature rise rate was 3 ° C./min, and the temperature range was from room temperature to 300 ° C.

Amount of gas generated: The amount of gas generated after heating and heating at 350 ° C. for 5 minutes using a sample heating gas generator manufactured by GL Science Co., Ltd. was measured by Hitachi Gas Chromatography G30.
It was measured at 00.

Adhesion: Each film cut into a width of 5 mm was placed on the prepared 42 alloy plate, and an electric heat press was used.
Preheating 350 ° C, 1 minute later, thermocompression bonding was performed for 20 seconds at 20 kg / cm ² , to obtain a test sample. Using this, Tensilon MPW-300S manufactured by Orientec Co., Ltd., JISC64
A 90 ° peeling test based on 81 was conducted to obtain an adhesive strength (g /
cm) was calculated.

[0053]

As described above, according to the block polyimide resin of the present invention, without passing through the intermediate amic acid,
By heat treatment in a polar solvent, the reaction is carried out by lactone-based catalytic polymerization and direct imidization is performed, so there are few ionic impurities, random copolymerization does not occur, and the original characteristics of each component can be fully exhibited. Is now possible.

Further, it is possible to easily form a block polyimide resin composition of multi-components, particularly four or more components, and to easily change the polymer of one component having insufficient mechanical strength or to add a polymer component having high mechanical strength. As a result, the mechanical strength can be supplemented without impairing other properties.

Furthermore, since a predetermined silicone diamine is introduced into the main chain of the polymer, it becomes possible to provide a block polyimide resin composition having excellent mechanical strength, heat resistance and low water absorption. It was

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenji Asano Inventor Kenji Asano 5-1-1 Hidaka-cho, Hitachi City, Ibaraki Prefecture, Hitachi Systems Co., Ltd. 5-1-1, Machi, Power Systems Research Laboratory, Hitsuritsu Cable Co., Ltd. (72) Inventor, Hiroshi Sugimoto, 3550, Kidayo-cho, Tsuchiura City, Ibaraki Prefecture, Hitachi, Ltd. System Materials Research Laboratory (56) References Flat 7-157560 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 73/00-73/26 CAPLUS (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] Claims : [Chemical 2] And [Chemical 3] And 3 types of aromatic diamine represented in, embedded image And [Chemical 5] A block polyimide resin comprising two types of acid dianhydride represented by and a silicone diamine. Wherein the absorption of the cured product is less than 1.0% claim 1, wherein the block polyimide resin. 3. A heated polar in the presence of a lactone catalyst.
## STR00006 ## in a solvent An aromatic diamine represented by : In reacted represented by dianhydride, further embedded image And [Chemical 9] An aromatic diamine represented by : Add an acid dianhydride represented by
Direct imidization can be achieved by sequential addition reactions that cause additional reactions.
A method for producing a block polyimide resin, comprising: