JPH06190981A - Laminated structural body - Google Patents

Abstract

PURPOSE:To make solubility to a solvent having a low boiling point favorable by lengthening a usable time and improving moisture resistance, by a method wherein a fresh heat-resistant laminated body is molded of a composition consisting mainly of a bisimide compound represented by a specific formula and a thermosetting oligomer represented by the other specific formula. CONSTITUTION:After adjustment of concentration of a polymer obtained by allowing the title method to knead a bisimide compound which is one side indisppensable constituent component of a blending resin composition to be used for a fresh heat-resistant laminated body and is represented by a formula I and a thermosetting oligomer which is the other indispensable constituent component of the blending resin composition and is represented by a formula II and/or a formula III within a solvent, a reinforcement material is coated and impregnated with this polymer solution. Then prepreg is made by drying the same so as to attain fixed residual solvent concentration and a fixed number of sheets of the made prepreg are molded integrally by heating and pressurizing them. Then the made prepreg is made into a B-stage.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat resistant laminate and a method for producing the same, and more particularly to a novel imide blend composition, a novel heat resistant laminate using the same as a matrix and a method for producing the same. More specifically, the present invention relates to an imide blend composition having a low moisture absorption rate, excellent mechanical strength and heat resistance, which is most suitable for lamination and molding, a novel heat-resistant laminate using the same, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the development of electronic equipment has been remarkable, and the use of copper-clad laminates has been diversified, and excellent properties are required. In particular, as the wiring density increases and the wiring board becomes multi-layered and the diameter of through holes is decreasing, a copper clad laminate with good workability, such as less smearing during drilling, is required. . On the other hand, with the demand for improved productivity and cost reduction, increasingly severe processing conditions such as hot air levelers and reflow soldering are being added in the wiring board mounting process. Among these, the heat resistance of the copper clad laminate that is the substrate,
Moisture resistance is required to be better than ever.

In order to meet these requirements, an epoxy resin, which is generally widely used as a resin for copper-clad laminates, has been replaced by an addition-curable polyimide resin in recent years. When this polyimide resin is used as a laminate for copper-clad laminates, it has the advantage that there is almost no smear during drilling, and that the heat resistance in the machining process and long-term tests is significantly improved. It has been known. However, conventionally used addition-curing type polyimide resins have various problems as described below.

That is, for example, a product obtained by reacting N, N'-bisimide of unsaturated dicarboxylic acid with diaminodiphenylmethane is excellent for a laminated plate, but on the other hand,
Diaminodiphenylmethane has a high reactivity and has a problem that the pot life is short when it is used as a varnish or when a prepreg is prepared. In addition, the toxicity of diaminodiphenylmethane to living organisms has sometimes been a problem.
Further, those containing N, N'-bisimide of unsaturated dicarboxylic acid and aminophenol as reaction components show well-balanced properties for laminates and have excellent processability but poor moisture resistance. There is a problem, for example, for long-term storage of the obtained laminate, special attention must be paid to moisture absorption.

Further, a product obtained by reacting an unsaturated dicarboxylic acid N, N'-bisimide with aminobenzoic acid is suitable for a laminated plate, but it has poor solubility in a low boiling point solvent and is not suitable for preparing a prepreg. However, there was a problem in applying it to a glass cloth or the like. Further, there is a problem in that the resin solution must be stored carefully.

[0006]

SUMMARY OF THE INVENTION The present inventors have arrived at the present invention as a result of intensive studies in order to solve these technical problems in view of such circumstances. The gist of the novel heat resistant laminate according to the present invention is that represented by the general formula (1)

[Chemical 7] (In the formula, Ar ₁ represents a tetravalent organic group. Ar ₂ represents a divalent organic group, and may be the same or different. M is a positive integer of 0 to 20. In addition, R ₁ represents a carbon-carbon unsaturated bond) and a bisimide compound represented by the general formula (2)

[Chemical 8] And / or the compound represented by the general formula (3) 9

[Chemical 9] (In the general formulas (2) and (3), Ar ' ₁ represents a tetravalent organic group, Ar' ₂ represents a divalent organic group, and Ar ' ₁ and Ar' ₂
May all be the same or different. Further, X represents a trivalent bonding mode,

[Chemical 10] And may be the same kind or different kinds. n represents a positive integer of 0-20. R ₂ represents a reactive functional group. ) Is formed by a composition containing a thermosetting oligomer represented by the formula (4) as a main component.

In such a novel heat-resistant laminate, the R ₁
But 11

[Chemical 11] Is at least one selected from the structures shown in.

In the novel heat resistant laminate, the R ₂ is

[Chemical 12] At least one selected from among the above.

Next, the gist of the method for producing a novel heat-resistant laminate according to the present invention is that the above-mentioned claim 1 to claim 3
In the method for producing the novel heat-resistant laminate according to any one of items 1 to 5, the concentration of the polymer solution obtained by kneading the bisimide compound and the thermosetting imide oligomer in a solvent is adjusted, and then the polymer solution is used as a reinforcing material. Is applied to and impregnated with, and then dried so as to have a predetermined residual solvent concentration to prepare a prepreg, and a predetermined number of the prepared prepreg is heated and pressurized to be integrally molded.

In addition, in the method for producing such a novel heat-resistant laminate, the prepreg thus prepared is B-staged.

[0011]

EXAMPLES Next, in explaining the examples of the novel heat-resistant laminate and the method for producing the same according to the present invention, first, the blended resin composition which is a constituent component of the novel heat-resistant laminate and the method for producing the same will be explained.

The compound represented by the general formula (2), which is one of the constituent components of the blended resin composition,

[Chemical 13] And / or Formula (3) 14

[Chemical 14] The thermosetting oligomer represented by and the method for producing the same will be described.

After drying the reaction vessel within a range that can be understood by those skilled in the art, it is replaced with an inert gas such as argon or nitrogen, and a predetermined amount of a non-aqueous polar solvent is charged. In an inert gas atmosphere, the compound represented by the general formula (4)

[Chemical 15] (In the formula, Ar ′ ₁ represents a tetravalent organic group.) Or a dianhydride represented by the general formula (5)

[Chemical 16] (In the formula, Y represents hydrogen or an alkyl group selected from 1 to 5 carbon atoms, and may be one kind or different.
₁ represents a tetravalent organic group, and may be one kind, or may be selected from multiple components. ) The acid dianhydride derivative represented by the formula (1) is dissolved in a polar organic solvent, and in the solution, a general formula (6) H ₂ N-Ar ′ ₂ —NH ₂ (6) (in the formula, Ar ′ ₂ is 2 A divalent organic group) is dissolved in the same polar solvent as described above or added as a powder while paying attention to heat generation and thickening. A base telechelic oligomer is obtained. The reaction temperature at this time is -15 to 120 ° C.
Is preferred, preferably -15 to 100 ° C, more preferably -5 to 50 ° C. The reaction time is preferably about 1 to 5 hours.

The reaction solution was converted to the general formula (7).

[Chemical 17] (In the formula, R ₂ represents a substituent having reactivity.) A primary amine having a heat-reactive group represented by the formula (8)

[Chemical 18] (In the formula, R ₂ represents a reactive substituent.) An acid anhydride having a heat-reactive group represented by the formula is added to terminate the terminal, and a precursor of a heat-curable oligomer having reactivity is added. Obtain the amic acid solution that is the body. The reaction temperature at this time is 0
The temperature is preferably 120 to 120 ° C, preferably 0 to 100 ° C, and more preferably 40 to 100 ° C. The reaction time is preferably about 1 to 5 hours. Then, add a non-solvent to thermally close and dehydrate the amic acid solution,
Convert to imide resin under reflux and azeotropy.

Here, the non-solvent used may be aromatic hydrocarbons such as xylene and toluene, but it is preferable to use toluene. The reaction is carried out by refluxing water that can be azeotropically distilled off using a Dean-Stark reflux device until a theoretical amount of water is collected. For the dehydration ring closure reaction to this imide structure, an applied method based on the knowledge of those skilled in the art can be used, such as using a chemical ring closure method together. After the reaction, the imide solution is poured into water or an alcohol solvent with vigorous stirring to precipitate the imide resin as a powder. After collecting the powder by filtration, for example, 80
Dried under reduced pressure at ℃ for 48 hours.

Next, the compound represented by the general formula (1), which is the other essential constituent of the blended resin composition used in the novel heat-resistant laminate according to the present invention, is represented by Formula 19

[Chemical 19] The bisimide compound represented by can be synthesized in the same manner as in the above-mentioned thermosetting oligomer synthesis method. further,
The bisimide compound represented by the general formula (1) can be used without any restriction within the range known to those skilled in the art.

[Chemical 20] A bisimide having the structure of can be exemplified.

Here, the synthesis of the bisimide compound represented by the general formula (1), which is a constituent of the blended resin composition which is the main component of the novel heat resistant laminate according to the present invention, and the general formula (2) or the general formula As the diamine component used for synthesizing the thermosetting oligomer represented by the formula (3), general formula (6) H ₂ N-Ar ′ ₂ —NH ₂ (6) (wherein, Ar ′ ₂ is a divalent group) The Ar ' ₂ group (Ar ₂ group) in the diamine compound represented by the formula ( ₄ ) is essentially any divalent organic group. 22, Chemical 23

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23] Etc. can be mentioned.

In particular, the Ar ' ₂ group (Ar ₂ group) is preferably an aromatic group.

[Chemical formula 24] It is preferable that at least one of the above is a main component.

As the organic tetracarboxylic dianhydride which can be used in the present invention as shown in the above-mentioned production method, organic tetracarboxylic dianhydrides having any structure can be used. The Ar ₁ group and Ar ′ ₁ group in the general formulas (1) to (3) are tetravalent organic groups, and particularly preferably aromatic groups.

Specific examples of this Ar ₁ group or Ar ′ ₁ group are shown below.

[Chemical 25]

[Chemical formula 26] Can be mentioned.

These organic tetracarboxylic dianhydrides may be used alone or in combination of two or more. More specifically, from the viewpoint of balancing various characteristics, 27

[Chemical 27] It is preferable to use at least one of the above as the main component.

Further, the aprotic polar organic solvent used in the reaction for producing the polyamic acid ester solution is, for example, an ether solvent such as tetrahydrofuran or dioxane, a sulfoxide-based solvent such as dimethyl sulfoxide or diethyl sulfoxide, N, N'-. Formamide solvents such as dimethylformamide, N, N'-diethylformamide, N, N'-dimethylacetamide, N,
Examples thereof include acetamide-based solvents such as N'-diethylacetamide. These may be used alone or as a mixed solvent of two or three or more. Furthermore, together with these aprotic polar solvents, acetone, methanol, isopropanol, benzenemethyl cellosolve, etc. can be used as a mixed solvent with the non-solvent of the polyamic acid ester solution.

Further, the oligomer used in the present invention can be used in combination with so-called B-stage formation, if necessary. The B-staging is carried out at 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher, for 1 minute or longer, preferably for 5 minutes or longer, under melting with hot air circulation or under vacuum.

Further, the mechanism of the thermosetting resin, which is the reactive blended resin composition used in the present invention, having particularly high heat resistance is not clear, but addition polymerization of acetylene / acetylene groups or tri- or tri- or acetylene group is not clear. Benzene skeleton formation by quantification, propargyl ether [3,3]
This is because a highly efficient polymer-forming reaction such as ring-opening / addition polymerization of a chromene ring, which is a sigmatropic transition product, and further addition copolymerization of acetylene and / or chromene and a carbon-carbon double bond of bisimide can be expected.

In order to control the number average degree of polymerization, n and m in the general formulas (1) to (3) are 0 to 30 or less, preferably 0 to 25 or less, more preferably 0 to 20 or less. Is good. If it is more than that, there is a drawback that the solubility in an organic solvent decreases.

The novel heat-resistant laminate, which is the composition of the present invention, contains the above-described reactive bisimide compound and thermosetting oligomer as essential essential components, but it is known as necessary. Epoxy resin and epoxy resin curing agents, curing accelerators, fillers, flame retardants, reinforcing agents, surface treatment agents, pigments, various elastomers, etc. can be used together.

The known epoxy resin is a compound having two or more epoxy (glycidyl) groups in the molecule. For example, bisphenol A, bisphenol F, hydroquinone, resorcin, flurglycine, tris- (4
-Hydroxyphenyl) methane-1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane and other divalent or trivalent phenols or novolaks derived from tetrabromobisphenol A or brominated polyphenols Novolak epoxy resins, aniline, para-aminophenol, meta-aminophenol, which are reaction products of glycidyl ether compounds, phenols, orthocresols, and other phenols derived from halogenated polyphenols with formaldehyde
Amino-metacresol, 6-amino-metacresol, 4,4'-diaminodiphenylmethane, 8,8'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether.
1,4-bis (4-aminophenoxy) benzene ・ 1,
4-bis (3-aminophenoxy) benzene ・ 1,3-
Bis (3-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, paraphenylenediamine, metaphenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, paraxylylenediamine Metaxylylenediamine ・ 1,4-cyclohexane-bis (methylamine) ・ 1,3-cyclohexane-bis (methylamine) ・ 5-amino-1-
(4'-Aminophenyl) -1,8,8-trimethylindane-6-amino-1- (4-aminophenyl)-
Amine-based epoxy resins derived from 1,8,8-trimethylindane and the like, glycidyl ester-based compounds derived from aromatic carboxylic acids such as paraoxybenzoic acid, terephthalic acid and isophthalic acid, 5,5-dimethylhindantoin And the like derived from the above, 2,2′-bis (3,4-epoxycyclohexyl) propane · 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane · vinylcyclohexenedioxide・ Alicyclic epoxy resin such as 3,4-epoxycyclohexanecarboxylate, etc.,
Examples thereof include triglycidyl isocyanurate · 2,4,6-triglycidoxy-s-triazine and the like, or two or more thereof.

Examples of known epoxy curing agents include amine curing agents such as aromatic amines and aliphatic amines such as xylylenediamine, polyphenol compounds such as phenol novolac and cresol novolac, and hydrazide compounds. As a curing accelerator, benzyldimethylamine-2,4,6-tris (dimethylaminomethyl)
Examples thereof include amines such as phenol / 1,8-diazabicycloundecene, imidazole compounds such as 2-ethyl-4-methylimidazole, and boron trifluoride amine complex.

It is also effective to add various elastomers based on the knowledge of those skilled in the art in order to improve the mechanical strength.

As described above, the novel heat-resistant laminate according to the present invention is a composition containing a bisimide compound and a thermosetting oligomer as essential components, and if necessary, known epoxy resin or epoxy resin cured Agents, curing accelerators, fillers, flame retardants, reinforcing agents, surface treatment agents, pigments, various elastomers, etc. are used together. The novel heat resistant laminate can be molded and used as it is, but it is usually dissolved in an organic solvent and used in the form of a prepreg.

In molding the prepreg, the resin concentration when the novel heat-resistant laminate according to the present invention is dissolved and diluted in an organic solvent is 5 to 75% by weight, preferably 15 to 65% by weight in view of the resin concentration in the prepreg. It is desirable to use it in the range of% by weight. It is preferable to adjust the residual solvent concentration of the prepreg in the range of 1 to 20% by weight, preferably 1 to 10% by weight, and more preferably 1 to 5% by weight in terms of solvent / resin ratio calculation. Below that, there arises a problem that the mechanical properties of the laminated plate after prepreg molding are lowered. Further, if it is more than that, there is a disadvantage that voids are generated because the residual solvent is volatilized during prepreg molding.

Next, a method for producing a heat resistant laminate using the heat resistant prepreg obtained as described above will be described.

The number of prepregs is adjusted so that the desired thickness is obtained. A predetermined prepreg is inserted between two stainless steel plates or dies whose surfaces are mirror-finished, and then heated and pressed for a predetermined time and under pressure to form a laminated plate having a predetermined thickness. At that time, it is also possible to adjust the amount of volatile gas by using a reduced pressure or a vacuum state together. Since the amount of volatile gas can be adjusted in this way, this resin system is also suitable for autoclave processing.

The novel heat-resistant laminate according to the present invention is so-called P
When used for WB (Printed Circuit Board) applications, various fillers and reinforcing agents can be applied in various ways based on the knowledge of those skilled in the art. Among them, examples of the filler include aluminum hydroxide, antimony trioxide, red phosphorus and the like. Further, as the reinforcing agent, carbon fiber, glass fiber, aramid fiber, liquid crystal polyester fiber such as Vectra, polybenzothiazole (PBT) fiber, alumina fiber, etc. woven cloth, non-woven cloth, mat, paper (paper) or a combination thereof. Can be illustrated. In addition, it is also effective to use after-cure together to improve the mechanical strength.

The use of the novel heat-resistant laminate according to the present invention is not limited, and it can be applied in various modes based on the knowledge of those skilled in the art. Among them, electric laminates, so-called P
It is also possible to use it as a matrix resin for WB.

Although the examples of the novel heat-resistant laminate according to the present invention have been described above along with the manufacturing method thereof, the present invention is not limited to these examples. Further, the examples of the present invention will be described in more detail below, but the present invention is not limited to these examples, and the present invention is within the scope of the gist of the person skilled in the art. Based on the above, various modifications, improvements and changes can be made.

Production Example 1 (Synthesis of 4-aminophenyl-1-propargyl ether) A 500-ml three-necked flask was equipped with a 200-ml dropping funnel, a three-way cock and a seal cap, dried under reduced pressure and replaced with argon. . 26.91 g (0.16 mol
4) Nitrophenyl-1-propargyl ether and 270 ml of dioxane were charged to a reaction vessel. 26
0.49 g (1.16 mol) of tin chloride and 270 ml of concentrated hydrochloric acid were added dropwise over 2 hours under ice cooling. The reaction solution was stirred for 1 hour while being cooled with ice, and then added dropwise to 1 liter of a 10 wt% sodium hydroxide aqueous solution. After filtering out the precipitated tin hydroxide, the filtrate was extracted from methylene chloride. After dehydration and filtration, the solvent was distilled off and the precipitated crystals were filtered out and recrystallized using toluene. As a result, 20.12g
(Yield: 89.2%) of 4-aminophenyl-1-propargyl ether was obtained.

[Elemental analysis value] Calculated value: C; 73.46, H; 6.12, N; 9.52 Actual value: C; 73.85, H; 5.98, N; 9.86

[Spectral data] IR (neat, cm ⁻¹ ) ν = 3600-3000,300
0,2950,1620,1600,1580,149
5,1450,1350,1295,1220,116
0,990,905,860,780,735,69
0. ¹ H-NMR (chloroform-d, ppm) δ = 2.5
(Tr., 1H), 3.5 (br.s., 2H), 4.75 (d.,
J = 1.2H _Z 1H), 6.7 (m., 4H)

Reference Example 1 A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock, and a seal cap, dried under reduced pressure and replaced with argon. 6.44 g (0.202 mol)
Of benzophenone tetracarboxylic acid dianhydride was charged into a reactor, and then 150 ml of dimethylformamide (hereinafter,
Abbreviated as DMF. ) Was added. 1.46g (0.005mo
l) 1,3-bis (3-aminophenoxy) benzene and 2.23 g (0.005 mol) 2,2-bis (4)
30 ml of -aminobenzoyloxyphenyl) propane
After being dissolved in DMF, was introduced into the reactor from a dropping funnel. After stirring at 80 ° C. for 2 hours, 2.75 g (0.0
2 mol) 4-aminophenyl-1-propargyl ether dissolved in 20 ml DMF were added. After the reaction temperature of the reactor was returned to room temperature, 11 ml of acetic anhydride and 10 ml of pyridine were added to the obtained oligo-amic acid to cause chemical dehydration and ring closure to obtain an imide oligomer. After the reaction, the reaction solution was poured into 1 liter of methanol to precipitate the produced imide oligomer. The mixture was filtered under reduced pressure with an aspirator and dried in vacuum at 80 ° C. for 48 hours to obtain 11.9 g (yield; 97.5%) of a thermosetting oligomer as a pale yellow powder.

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, 178
0,1750,1700,1620,1600,158
0,1495,1450,1350,1295,122
0,1160,990,905,860,780,73
5,690.

Reference Example 2 A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock, and a seam cap, dried under reduced pressure and replaced with argon. 6.44 g (0.202 mol)
Benzophenonetetracarboxylic dianhydride was charged to the reactor and 150 ml of DMF was added. 1.46g
(0.005 mol) 1,3-bis (3-aminophenoxy) benzene and 2.23 g (0.005 mol) 2,2-bis (4-aminobenzoyloxyphenyl)
Propane was dissolved in 30 ml of DMF and then introduced into the reactor through a dropping funnel. After stirring at 80 ° C for 2 hours,
2.85 g (0.02 mol) of 3-aminophenoxy-
1-Propene was dissolved in 20 ml DMF and added. After the reaction temperature of the reactor was returned to room temperature, 11 ml of acetic anhydride and 10 ml of pyridine were added to the obtained oligoamic acid, and the mixture was chemically dehydrated and ring-closed to obtain an imide oligomer. After the reaction, the reaction solution was poured into 1 liter of methanol to precipitate the produced imide oligomer. When filtered under reduced pressure with an aspirator and dried in vacuum at 80 ° C. for 48 hours, 11.9 g (yield; 97.
A thermosetting oligomer was obtained as a pale yellow powder (5%).

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, 178
0,1750,1700,1620,1600,158
0,1495,1450,1350,1295,122
0,1160,990,905,860,780,73
5,690.

Reference Example 3 A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock, and a seal cap, dried under reduced pressure and replaced with argon. 6.44 g (0.202 mol)
Benzophenonetetracarboxylic dianhydride was charged to the reactor and 150 ml of DMF was added. 1.46g
(0.005 mol) 1,3-bis (3-aminophenoxy) benzene and 2.23 g (0.005 mol) 2,2-bis (4-aminobenzoyloxyphenyl)
Propane was dissolved in 30 ml of DMF and then introduced into the reactor through a dropping funnel. After stirring at 80 ° C for 2 hours,
4.08 g (0.02 mol) of propargyl ether phthalic anhydride dissolved in 20 ml of DMF were added. After the reaction temperature of the reactor was returned to room temperature, the obtained oligoamic acid was chemically dehydrated and ring-closed by adding 11 ml of acetic anhydride and 10 ml of pyridine to obtain an imide oligomer.
After the reaction, the reaction solution was poured into 1 liter of methanol to precipitate the produced imide oligomer. When filtered under reduced pressure with an aspirator and dried in vacuum at 80 ° C. for 48 hours, 11.9 g (yield: 84.5
%) As a pale yellow powder to give a thermosetting oligomer.

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, 178
0,1750,1700,1620,1600,158
0,1495,1450,1350,1295,122
0,1160,990,905,860,780,73
5,690.

Example 1 27.5 g of bisimide [MB-80 manufactured by Mitsubishi Petrochemical Co., Ltd.]
00] and 27.3 g of the thermosetting oligomer synthesized in Reference Example 1 were introduced into a reactor charged with 200 ml of DMF. After stirring and reacting at room temperature for 2 hours, 8 pieces of 10 × 15 cm glass cloth (using WEA18W manufactured by Nitto Boseki Co., Ltd.) were impregnated. When dried in a circulating oven at 150 ° C. for 2 hours, a prepreg having a resin content of 42% by weight was obtained. Then, the obtained prepreg is treated with 23
B-stage at 0 ° C for 10 minutes, and use the prepreg for 0.5 hours at 150 ° C, 1 hour at 230 ° C, 260
By press molding at a pressure of 50 kg / cm @ 2 for a cycle of 2 hours at .degree. C., a laminated plate having a thickness of 1.5 mm was obtained. The evaluation results are shown in Table 1.

[Table 1]

Example 2 27.5 g of bisimide [MB-80 manufactured by Mitsubishi Petrochemical Co., Ltd.]
00] and 27.8 g of the thermosetting oligomer synthesized in Reference Example 2 were introduced into a reactor charged with 200 ml of DMF. After stirring and reacting at room temperature for 2 hours, the mixture was processed under the same conditions as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm. The evaluation results are shown in Table 1.

Example 3 27.5 g of bisimide [MB-80 manufactured by Mitsubishi Petrochemical Co., Ltd.]
00] and 27.8 g of the thermosetting oligomer synthesized in Reference Example 3 were introduced into a reactor charged with 200 ml of DMF. After stirring and reacting at room temperature for 2 hours, the mixture was processed under the same conditions as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm. The evaluation results are shown in Table 1.

Comparative Example 1 Using Kelimide 601 (purchased from Nippon Polyimide Co., Ltd.), 95 g thereof was dissolved in 120 g of DMF (resin concentration; 45% by weight / DMF). It was dried at 120 ° C. for 85 minutes in a hot air circulation drying furnace to prepare a prepreg having a resin concentration of 40.2% by weight and a residual solvent concentration of 6.4%. Use 8 sheets of prepreg made at 220 ℃ for 2 hours, 2
Heat and pressure are integrally molded at a pressure of 5 kg / cm ² to obtain a plate thickness of 5.
A 7 mm laminated plate was obtained. The evaluation results are shown in Table 1.

Comparative Example 2 165 g of imide oligomer thermid MC-600 (purchased from Kanebo NSC Co., Ltd.) was dissolved in 200 g of DMF (resin concentration: 45% by weight / DMF). It was dried at 120 ° C. for 85 minutes in a hot air circulation drying furnace to prepare a prepreg having a resin concentration of 31.2% by weight and a residual solvent concentration of 9.4%. 220 ° C using 8 prepregs
By heat and pressure integral molding for 2 hours at a pressure of 25 kg / cm ² , a laminate having a plate thickness of 6.2 mm was obtained. The evaluation results are shown in Table 1.

[0051]

EFFECT OF THE INVENTION The novel heat-resistant laminate according to the present invention is formed from a composition containing a predetermined bisimide compound and a thermosetting oligomer as main components, and the obtained novel heat-resistant laminate has excellent processability. , Had extremely high heat resistance. Furthermore, the novel heat-resistant laminate according to the present invention not only has excellent mechanical strength, but also has low hygroscopicity, excellent dimensional stability, and electrical characteristics.

Further, according to the method for producing a novel heat-resistant laminate of the present invention, it has excellent moisture resistance and heat resistance with high industrial value,
Further, it is possible to produce a laminated body such as a laminated board in which defects such as voids and cracks are hard to occur, which is extremely useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C08G 73/10 NTF 9285-4J

Claims (5)

[Claims] 1. A compound represented by the general formula (1): (In the formula, Ar ₁ represents a tetravalent organic group. Ar ₂ represents a divalent organic group, and may be the same or different. M is a positive integer of 0 to 20. R ₁ represents a carbon-carbon unsaturated bond) and a bisimide compound represented by the general formula (2): And / or Formula 3 (3) (In the general formulas (2) and (3), Ar ' ₁ represents a tetravalent organic group, Ar' ₂ represents a divalent organic group, and Ar ' ₁ and Ar' ₂
May all be the same or different. Further, X represents a trivalent bonding mode, and And may be the same kind or different kinds. n represents a positive integer of 0-20. R ₂ represents a reactive functional group. ) A novel heat-resistant laminate, characterized by being molded from a composition comprising a thermosetting oligomer represented by (4) as a main component. 2. The R ₁ is represented by the following formula: The novel heat-resistant laminate according to claim 1, which is at least one kind selected from the structures shown in. 3. The R ₂ is represented by the following formula: It is at least 1 sort (s) selected from among these, The novel heat resistant laminated body of Claim 1 or Claim 2 characterized by the above-mentioned. 4. A polymer solution obtained by kneading the bisimide compound and a thermosetting imide oligomer in a solvent in the method for producing the novel heat-resistant laminate according to any one of claims 1 to 3. After adjusting the concentration of the prepreg, the polymer solution is applied to and impregnated into the reinforcing material, and then dried to obtain a predetermined residual solvent concentration to prepare a prepreg, and a predetermined number of the prepared prepreg is heated and pressed. A novel method for producing a heat-resistant laminate, which comprises integrally molding. 5. The method for producing a novel heat-resistant laminate according to claim 4, wherein the prepared prepreg is B-staged.