JP3446561B2 - Block polyimide resin, resin solution 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 producing the same, and more particularly to a new type block polyimide resin having a small amount of ionic impurities that can be used as a material for electronic devices and a method for producing 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.
JP-A-21165 describes a method for producing a polyimide resin of a copolymer by a sequential addition method. In this method, first, an excess amount or an excessive amount of an acid dianhydride is added to an aromatic diamine to cause a reaction, and a polyamic acid prepolymer is produced. Next, to this polyamic acid prepolymer, a shortage of diamine is added to produce a polyamic acid copolymer, and this is subjected to chemical treatment or heat treatment to produce a copolymer polyimide resin. .

Further, Japanese Patent Application Laid-Open No. 1-211165 discloses that
A method of making a film of polyimide resin is described. In this method, first, 1.5 to 2.0 mol% of an acid dianhydride is added to a diamine in a polar solvent and reacted at a low temperature to synthesize an amic acid oligomer. In this oligomer,
An equal amount of isocyanate is added and reacted to generate polyimide amide carboxylic acid while generating carbon dioxide gas, and the polyimide amide carboxylic acid is cast and heated,
We are making a film of polyimide resin.

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
A method for producing a polyimide resin of a siloxane-amic acid block copolymer is described. This method starts with
An acid dianhydride is added to the diaminosiloxane copolymer to form a siloxane-amic acid block copolymer. An equal amount of diamine is added to the siloxane-amic acid block copolymer to form a polyamic acid, which is chemically treated or heat-treated to produce a siloxane-imide block copolymer polyimide resin.

US Pat. No. 4,011,279 describes block-polyimide resins of polyimide-polyorganosiloxane prepared using organic acid catalysts.

In Japanese Patent Laid-Open No. 4-50579,
A polyamic acid is produced from a bicyclooct-ene-tetracarboxylic dianhydride derivative and a bismaleimide compound, and a polyimide resin, which is an adhesive resin composition, is produced from this polyamic acid.

The polyimide resins disclosed in JP-A-2-91124, US Pat. No. 4,011,279, and JP-A-4-50579 have excellent adhesion to substrates.

Further, JP-A-4-306232 describes a method for producing a solvent-soluble polymer precursor having an amic acid segment via a polyamic acid. This precursor is composed of a first segment and a second segment, and each segment is produced from different diamines and amic acid, which is a product of acid dianhydride, to the extent that polyamic acid exchange reaction does not occur. It is imidized.

According to Japanese Patent Application Laid-Open No. 4-306232, since the polyamic acid is imidized to the extent that it does not undergo an exchange reaction, a stable polyimide resin having excellent blockability can be obtained.

US Pat. No. 5,502,143 describes a method for producing a three-component polyimide resin that does not pass through a polyamic acid. This method uses γ-valerolactone as a catalyst to generate a polyimide oligomer from a first acid dianhydride and a diamine, and by sequentially adding a second and a third acid dianhydride and a diamine to the polyimide oligomer, A block polyimide resin is prepared.

According to the US Pat. No. 5,502,143, a stable polyimide resin having excellent blocking property can be obtained. Further, since it does not pass through a polyamic acid, the polyimide resin can be directly obtained by a one-step reaction. Can be simplified.

[0019]

However, JP-A-60-166326, JP-A-64-1683, JP-A1-211165, and JP-A-2-9112 are known.
According to the conventional method for producing a polyimide resin as disclosed in Japanese Patent Laid-Open No. 4 and Japanese Patent Laid-Open No. 4-50579, and US Pat. The generated high molecular weight polyamic acid is unstable to heat, and water generated by heat promotes hydrolysis to cause breakage of the molecular chain,
Recondensation at the imidization stage shows random copolymerizability,
There is a problem that the characteristics are inferior to those of each constituent.

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 method for producing a polyimide resin as disclosed in Japanese Patent Application Laid-Open No. 4-306232, since it is a two-step polycondensation method via polyamic acid,
There is a problem that the polyimide resin cannot be directly produced in the one-step reaction.

Further, according to the conventional polyimide resin as shown in US Pat. No. 5,502,143, since it is a three-component copolymerized polyimide resin, its physical and chemical characteristics are three components. There was a problem that it was regulated by the characteristics.

Therefore, an object of the present invention is to provide a multi-component block polyimide resin having a small amount of ionic impurities and high adhesiveness, which is different from the conventional random copolymerization polyimide resin and block copolymerization polyimide resin, and the same. It is to provide a manufacturing method.

[0024]

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] Which is obtained by reacting two types of acid dianhydrides, and has a weight molecular weight (polystyrene conversion) of 20,000 to 100,
000, and the content of ionic impurities is 0.1
Provided is a block polyimide resin characterized by having an adhesive property of not more than ppm.

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] There is provided a method for producing a block polyimide resin, characterized in that direct imidization is carried out by a sequential addition reaction in which an acid dianhydride represented by

[0026]

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.

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 toluene, xylene, tetralin, etc. are added to remove water out of the system by azeotropy, the imidization reaction is promoted and a high molecular weight polyimide is obtained. A resin can be obtained.

The present invention is a sequential addition reaction method in which an aromatic diamine is reacted with an acid dianhydride in a heated polar solvent in the presence of a lactone catalyst, and the aromatic diamine and the acid dianhydride are further added. It produces a block polyimide resin of 4 components or more in stages, can prevent random copolymerization due to conversion reaction between amic acids, can sufficiently exhibit the original characteristics of each component, and is suitable for various applications. Can be obtained. For example, by replacing a 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 solution 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 coating thickness of the varnish and 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 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 when it is less than 20% by weight, it is difficult to make the coating film thick, and 40% by weight is obtained.
If it exceeds, the viscosity of the varnish becomes high and the coating property becomes poor.

[0035]

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.

[Table 1]

Example 1 A stirrer and a condenser tube with a ball are attached to a 1000 ml separable three-necked flask for producing a block polyimide resin composition. 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 air-cooled to obtain 29.42 g.
3,4,3,4-biphenyltetracarboxylic dianhydride (BPDA), 17.3 g of bis [4- (3-aminophenoxine) phenyl] sulfone (BAPS), 1
6.4 g 2,2-bis [4- (4-aminophenoxine) phenyl] propane (BAPP), 160 g NM
P 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 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 ^-1 , 1
The characteristic absorption of imide was observed at 721 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 tougher than the conventional one. Could be made. Moreover, when the molecular weight of the varnish was examined using gel permeation chromatography (GPC), it was Mw (polystyrene conversion) = 55,000. Furthermore, varnish 25
When heated at 0 ° C for 2 hours and examined for the solid content, 2
It was 0.5%.

<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, 120 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 29.42 g.
BPDA, 17.3 g BAPS, 16.4 g BA
PP, 92 g of NMP, and 30 g of toluene were added, the temperature was raised again to 180 ° C., and the mixture was stirred and reacted for 4.5 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 directly on a glass substrate, dried at 150 ° C., peeled off from the glass substrate, and heat-treated at 250 ° C. to obtain a tougher film than the conventional one. It was possible to make. Moreover, when the molecular weight of the varnish was investigated using GPC, it was Mw (polystyrene conversion) = 57100.
Furthermore, the varnish was heated at 200 ° C. for 2 hours, and the solid content thereof was examined and found to be 30.3%.

<Embodiment 3> 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, 120 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, this reaction solution was air-cooled to obtain 32.36 g.
BPDA, 17.3 g BAPS, 16.4 g BA
PP, 92 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 6 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 obtain a tougher film than the conventional one. It was possible to make. Moreover, when the molecular weight of the varnish was examined using GPC, it was Mw (polystyrene conversion) = 77300.
Furthermore, the varnish was heated at 250 ° C. for 2 hours, and the solid content thereof was examined and found to be 30.1%.

<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, 120 g of NMP, and 30 g of toluene were added, and the mixture was stirred at room temperature in a nitrogen atmosphere with a stirrer for 10 minutes. 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 32.36 g.
BPDA, 17.3 g BAPS, 16.4 g BA
PP, 92 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 2 hours with a stirrer to form a varnish. At this time, the rotation speed of the stirrer is initially set to 150 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., and then peeled off from the glass substrate. When the film was peeled off, the film was gradually cut, and was tough. It was not possible to make a perfect film. Moreover, when the molecular weight of the varnish was examined using GPC, Mw (polystyrene conversion) = 1
It was 4600.

<Comparative Example 2> 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, 120 g of NMP, and 30 g of toluene were added, and the mixture was stirred at room temperature in a nitrogen atmosphere with a stirrer for 10 minutes. 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, this reaction solution was air-cooled to obtain 32.36 g.
BPDA, 17.3 g BAPS, 16.4 g BA
PP, 92 g of NMP, and 30 g of toluene were added, the temperature was raised to 180 ° C. again, and the mixture was stirred at 180 rpm
The mixture is reacted with stirring at m for 4 hours to form a varnish. Further, the water produced during the reaction is removed from the silicon cock.

A part of this varnish is directly cast on a glass substrate, 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, Mw (polystyrene conversion) = 155200
Met.

<Comparative Example 3> Ricacoat PN20 (3,3 ', 4,4'-diphenylsulfone / tetracarboxylic acid = polyimide, which is a ready-made varnish manufactured by Shin Nippon Rika Co., Ltd., is cast on a glass substrate. Then, after drying at 150 ° C., peeling it off from the glass substrate,
A film is prepared by heat treatment at 0 ° C.

The results of measuring the properties of the block polyimide resins produced in the examples and comparative examples are shown in Table 2. In Comparative Example 1, the film could not be produced, and therefore the measurement of characteristics was impossible, and the result was not displayed.

[0055]

[Table 2]

The evaluation of various characteristics shown in Table 2 is performed by 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 Denshi Kogyo Co., Ltd.
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 Denshi Kogyo 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 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: 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.

Gas generation rate: Using a sample heating gas generation apparatus manufactured by GL Science Co., Ltd., the generated gas quantity after heating and heating at 350 ° C. for 5 minutes 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.

[0066]

As described above, according to the block polyimide resin of the present invention and the method for producing the same, a lactone-based catalytic polymerization reaction is achieved by heat treatment in a polar solvent without passing through an intermediate amic acid. Since the imidization is carried out directly, random copolymerization does not occur, and the original characteristics of each constituent component can be sufficiently exhibited.

Further, since the imidization is carried out directly, the amount of ionic impurities is small, the reaction solution can be used as it is as a varnish, and the solid content of the varnish can be adjusted to a desired value at the raw material charging stage, which results in high adhesiveness. In the field of electronic parts such as semiconductors, the film thickness can be freely adjusted, and the coating thickness of the varnish between the substrate and the chip can be freely adjusted to make the film thicker. Touch can now be prevented.

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

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenji Asano Kenji Asano 5-1-1, Hidaka-cho, Hitachi-shi, Ibaraki Power Systems Laboratory, Hitachi Cable, Ltd. (72) Inventor Hideki Yagyu Hidaka, Hitachi-shi, Ibaraki 5-1-1, Machi, Power Systems Laboratory, Ritsudden Cable Co., Ltd. (72) Inventor, Hiroshi Sugimoto, 3550, Kidayomachi, Tsuchiura City, Ibaraki Prefecture Hitachi Cable, Ltd. System Materials Laboratory, (72) Inventor, Hiroshi Itaya Room No. 202, No. 1-225, Minato-Nitta, Ichikawa City, Chiba Prefecture (72) Inventor Shunichi Matsumoto, No. 2-51, Tsunishi 2-chome, Kamakura City, Kanagawa Prefecture (56) Reference JP-A-7-157560 (JP, A) ( 58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 73/00-73/26 C08L 79/00-79/08 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] Which is obtained by reacting two types of acid dianhydrides and has a weight molecular weight in the range of 20,000 to 100,000,
A block polyimide resin having an ionic impurity content of 0.1 ppm or less and having adhesiveness. Wherein said components of the block polyimide resin will be reacted in a polar solvent, the solids content 20-4
0 block of claim 1, wherein the percentages by weight
Block polyimide resin solution using black 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 : In the sequential addition reaction in which the acid dianhydride represented by
Block poly characterized by direct imidization
Method for producing imide resin.