JPH04222861A - Polyimide resin composition, prepreg and laminate thereof - Google Patents

Abstract

PURPOSE:To obtain a polyimide resin composition and prepreg thereof capable of producing laminates having excellent through-hole reliability and low dielectric constant, comprising a polyimide resin, an allyl group-containing bisphenol A derivative, a promoter, a solvent, etc. CONSTITUTION:A resin composition comprising (A) 100 pts.wt. polyimide resin obtained by reacting an unsaturated bis-imide with a diamine, containing >=11wt.% preferably at least one of alkyl and alkylene except methylene in the polyimide resin, (B) 10-200 pts.wt. allyl group-containing bisphenol A derivative, preferably an allyl ether of bisphenol A and/or diallyl bisphenol A, (C) a promoter and a solvent and preferably for flame retardance (D) 1-50 pts.wt. calculated as bromine content of a reactive group-containing brominated resin (preferably brominated epoxy resin). The composition is impregnated into a material and semicured to give prepreg. The prepreg is laminated and cured to give a laminate.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a polyimide resin composition used for printed wiring boards, etc., a polyimide resin prepreg using this resin composition, and a polyimide resin laminate obtained by curing this prepreg. be.

0002

2. Description of the Related Art Polyimide resins and epoxy resins have been widely used as resins for laminated boards and the like. Among these, polyimide resins have been widely used in highly multilayer wiring boards for high-density packaging, as described in Japanese Patent Laid-Open Nos. 59-20659 and 61-40322.

However, in recent years, the dielectric constant of polyimide resin laminates has been reduced in order to increase the propagation speed of electrical signals in response to the increasing speed of computers and other electromechanical devices using semiconductor devices. As the number of layers increases, there is a strong desire to prevent penetration of through-hole plating in order to improve reliability, and to improve safety.

0004

[Problems to be Solved by the Invention] The present invention aims to reduce the dielectric constant of a laminate in order to adapt to higher propagation speeds of electrical signals, and to improve the through-hole reliability of resin base materials. A polyimide resin composition that can ensure good impregnability, prevent penetration of through-hole plating, and further improve safety due to flame retardancy, a prepreg thereof,
and to provide a laminate thereof.

[0005]

[Means for Solving the Problems] The present invention has been made in view of the above points. The present inventors conducted research on reducing the dielectric constant of commonly known addition-type polyimide resins, and as a result, discovered a chemical structure effective for lowering the dielectric constant and its quantitative contribution. In addition, it has been found that when a predetermined amount of a bisphenol A derivative having an allyl group is blended, the dielectric constant further decreases. In addition,
By using a derivative of bisphenol A having an allyl group, the intrinsic viscosity of the resin decreases, a homogeneous and stable prepreg can be obtained, and a laminate with a low dielectric constant and excellent throughhole reliability can be obtained. They have discovered a polyimide resin composition and its prepreg that can be used. Furthermore, by blending a predetermined amount of brominated resin with reactive groups, it does not cause side effects such as reduced adhesion or heat resistance, and has flame retardant, low dielectric constant, and excellent through-hole reliability. We have discovered a polyimide resin composition and its prepreg that can be used to produce laminates.

[0006] The polyimide resin composition includes 1) a polyimide resin, and 2) 1 part by weight per 100 parts by weight of the polyimide resin.
It is characterized by consisting of a bisphenol A derivative having an allyl group, which is blended in an amount ranging from 0 to 200 parts by weight, 3), an accelerator, a solvent, etc. In order to achieve this, a brominated resin having a reactive group in a bromine content range of 1 to 50 parts by weight is blended with 100 parts by weight of the polyimide resin.

[0007] Furthermore, polyimide resin prepreg has 1
) polyimide resin, 2) a derivative of bisphenol A having an allyl group, which is blended in an amount ranging from 10 to 200 parts by weight per 100 parts by weight of the polyimide resin, 3)
And, it is characterized by impregnating a base material with a polyimide resin composition consisting of an accelerator, a solvent, etc. and semi-curing it.Furthermore, in order to obtain flame retardance, It is characterized in that it contains a brominated resin having a reactive group in a range of 1 to 50 parts by weight based on the bromine content.

[0008] The polyimide resin laminate also contains 1) a polyimide resin, and 2) bisphenol A having an allyl group, which is blended in an amount ranging from 10 to 200 parts by weight per 100 parts by weight of the polyimide resin. one or more semi-cured prepregs obtained by impregnating a base material with a polyimide resin composition consisting of a derivative of 3), an accelerator, a solvent, etc.,
It is characterized by being laminated and cured, and in order to obtain flame retardancy, bromine having a reactive group in the range of 1 to 50 parts by weight of bromine per 100 parts by weight of the polyimide resin is added. It is characterized by containing a chemical resin.

[0009] These will be explained in detail below. Polyimide resins can be obtained by reacting unsaturated bis-imides with diamines and the like. In the polyimide resin obtained in this way, at least one of an alkyl group or an alkylene group other than a methylene group is added to the polyimide resin.
The content is preferably 1% by weight or more. This is because if the chemical structure includes less than 11% by weight of alkyl groups or alkylene groups other than methylene groups in the resin molecule, the dielectric constant of the polyimide resin cannot be lowered.

The unsaturated bis-imide is represented by (a) in Chemical Formula 1 at the end of the specification, in which D represents a divalent group containing a carbon-carbon double bond, and A represents at least two Diamines are represented by the following formula (b), and B in formula (b) is a divalent group having 30 or less carbon atoms. Can be used. H2 NB-NH2 (b
) Note that A in formula (a) and B in formula (b) may be the same or different and may be a linear or branched alkylene group having fewer than 13 carbon atoms or a ring group. It can also be a cyclic alkylene radical having 5 or 6 carbon atoms in the radical, a heterocyclic radical containing at least one of O, N and S atoms, or a phenylene or polycyclic aromatic radical. These various groups may have substituents that do not cause unnecessary side reactions under the reaction conditions of a reaction temperature of 70 to 170°C and a reaction time of 30 to 350 minutes.

A in formula (a) and B in formula (b) also represent a number of phenylene groups or alicyclic groups bonded directly or by divalent atoms or groups such as You can also do that. For example, are they oxygen or sulfur?
An alkylene group of 1 to 3 carbon atoms or one of the following groups:

-NR4 -, -P(O)R3 -, -N
=N-, -O=N-, -CO-O-, -CONH-
, -SiR3 R4-, -NY-CO-X-CO-
NY-, -O-CO-X-CO-O-, -SO2 -,
and one of the group of chemical formula (c) at the end of the specification.

In these formulas, R3, R4 and Y each have 1 to 4 carbon atoms, and each has 5 carbon atoms in the ring.
represents a cyclic alkyl group having 1 or 6 carbon atoms, or a phenyl or polycyclic aromatic group, where X is a straight-chain or branched alkylene group having fewer than 13 carbon atoms, It represents a cyclic alkylene group having 5 or 6 carbon atoms, or a monocyclic or polycyclic arylene group.

The group D in formula (a) above is derived from the ethylene anhydride of chemical formula 1 (d) at the end of the specification, such as maleic anhydride, citraconic anhydride, tetrahydrocarbon anhydride, etc. It can also represent phthalic anhydride, itaconic anhydride, and the product of a Diels-Alder reaction between a cyclodiene and one of these anhydrides.

Preferred unsaturated bis-imides of formula (a) that can be used include:

Maleic acid N·N-ethylene-bis-imide, maleic acid N·N-hexamethylene-bis-imide, maleic acid N·N-metaphenylene-bis-imide,
Maleic acid N.N-paraphenylene-bis-imide, maleic acid N.N-4.4-diphenylmethane-bis-imide [usually also referred to as N.N-methylenebis (N-phenylmaleimide)], maleic acid N.・N-4・4-
Diphenyl ether bis-imide, maleic acid N/N
-4,4-diphenylsulfone-bis-imide, maleic acid N・N-4,4-dicyclohexylmethane-bis-imide, maleic acid N・N-α・α-4,4-dimethylenecyclohexane-bis-imide , maleic acid N・N
- metaxylylene-bis-imide, maleic acid N/N-
Diphenylcycloxane-bis-imide, 1,3-bis(2-p-anilinopropylidene)benzene-bis-imide, 1,4-bis(2-p-anilinopropylidene)
Benzene-bis-imide, 1,4-bis(2-m-anilinopropylidene)benzene-bis-imide, 4,4-
Methylenedi-2,6-xylidine-bis-imide, 4.
4-methylenedi-2,6-diethylaniline-bis-imide, 4,4-diamino-3,3-diethyl-5,5-
Dimethyldiphenylmethane-bis-imide, 4,4-methylenedi-2,6-diisopropylaniline-bis-imide, 2,5-dimethyl-p-phenylenediamine-bis-imide, 2,2-bis(4-aminophenyl) Propane-bis-imide, 2,4-diaminomesitylene-bis-imide, 3,5-diethyl-2,4-tolylenediamine-bis-imide, and the like.

Examples of diamines of formula (b) that can be used include the following: 4,4-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, metaphenynediamine, paraphenynediamine, 4,4-diaminodiphenylmethane, 2,2-bis-(4-aminophenyl) ) Propane, benzidine, 4,4-diaminophenyl oxide, 4,4-diaminodiphenyl sulfide, 4,4-
Diaminodiphenylsulfone, bis-(4-aminophenyl)diphenylsilane, bis-(4-aminophenyl)methylphosphine oxide, bis-(3-aminophenyl)methylphosphine oxide, bis-(4-
(aminophenyl) phenylphosphine oxide, bis-(4-aminophenyl) pheniramine, 1,5-diaminonaphthalene, meta-xylylene diamine, para-xylylene diamine, 1,1-bis-(para-aminophenyl)
Phthalane, hexamethylene diamine, 1,3-bis(2
-p-anilinopropylidene)benzene, 1,4-bis(2-p-anilinopropylidene)benzene, 1,4-
Bis(2-m-anilinopropylidene)benzene, 4.
4-methylenedi-2,6-xylidine, 4,4-methylenedi-2,6-diethylaniline, 4,4-diamino-
3,3-diethyl-5,5-dimethyldiphenylmethane, 4,4-methylenedi-2,6-diisopropylaniline, 2,5-dimethyl-p-phenylenediamine, 2.
2-bis(4-aminophenyl)propane, 2,4-diaminomesitylene, and 3,5-diethyl-2,4
- Tolylene diamine etc.

An addition type polyimide resin can be prepared by reacting the above bis-imide with a diamine. The molar ratio of bis-imide and diamine is 1 part bis-imide to 1 part diamine.
The range of 7 to 2.5 is preferable. If the bis-imide content is less than 1.7, the production of high molecular weight increases, resulting in a short curing time, which tends to cause problems in handling, while if the bis-imide content is more than 2.5, a large amount of unreacted raw material remains. It becomes easier to do. The reaction involves combining bis-imide and diamine with N-methylpyrrolidone (NMP) or N,N-dimethylacetamide (DM).
It can be carried out in a state dissolved in a solvent such as Ac), and the heating temperature during the reaction can be carried out in the range of about 70 to 170°C, and the reaction time can be carried out in the range of about 30 to 350 minutes. be able to.

As derivatives of bisphenol A having an allyl group, allyl ethers of bisphenol A (hereinafter referred to as BPA), such as BPA manufactured by Mitsui Toatsu Co., Ltd.
-AE, diallylbisphenol A, such as BPA-CA manufactured by Mitsui Toatsu Co., Ltd., can be used. These are preferable because they are liquid and suitable for use in varnishes, and their volatility is suitable for manufacturing conditions.

The polyimide resin composition of the present invention includes 100 parts by weight (hereinafter referred to as "parts") of the above-mentioned polyimide resin mixed with an amount ranging from 10 to 200 parts by weight of a BPA derivative having an allyl group; , imidazo- as accelerator
and organic peroxides, dimethylformamide (DMF), DMAc, dioxane, NMP as diluting solvents.
, MEK, etc., used alone or in combination. B having an allyl group
When the amount of the PA derivative added increases, the dielectric constant of the resulting laminate tends to decrease; when less than 10 parts is added, there is almost no effect of lowering the dielectric constant, and when more than 200 parts are added, the dielectric constant of the resulting laminate tends to decrease. This lowers the dielectric constant, but the laminate becomes hard and brittle, which is not preferable. In addition, these allyl group-containing BPA derivatives also act as reactive diluents, thereby lowering the intrinsic viscosity and surface tension of the resin composition. Therefore, the resin composition penetrates well between the fibers of the base material, and it is possible to obtain a prepreg in which the filling of the resin into the base material is significantly improved. In the laminates cured with this prepreg, the penetration length of the through-hole plating is significantly shortened, and at the same time, the inner walls of the through-holes are finished extremely smooth, which improves the insulation between the through-holes and the inner layer circuits. Effects such as ensuring properties and significantly improving the reliability of the through hole can be obtained.

[0021] In order to ensure the flame retardancy required for the safety of electronic mechanical devices, it is necessary to blend a brominated resin having a reactive group as a flame retardant into the polyimide resin composition. The blending amount of the brominated resin having the following is 1 to 50 parts by weight of bromine per 100 parts by weight of the polyimide resin.
It is necessary to use within the range of parts by weight. This is because if the amount is less than 1 part by weight, flame retardancy cannot be obtained, and if it is used in excess of 50 parts by weight, the heat resistance of the resulting laminate will deteriorate, the dielectric constant will increase, and the performance will deteriorate. be. In addition, the brominated resin must have a reactive group because the flame retardant is reacted with the side chains and terminal groups of the polyimide resin and incorporated into the skeleton of the polyimide resin structure, thereby increasing the interlayer adhesive strength. This is because it is possible to obtain a product that combines throughhole reliability, heat resistance, and flame retardant performance.

[0022] Therefore, as a reactive group, an epoxy group,
Alkyl of 1 to 4 carbon atoms with allyl group, vinyl group, etc., cyclic alkyl with 5 or 6 carbon atoms in the ring, or phenyl or polycyclic aromatic, or less than 13 carbon atoms A brominated resin such as a linear or branched alkylene having atoms, a cyclic alkylene having 5 or 6 carbon atoms in the ring, or a monocyclic or polycyclic arylene can be used as appropriate. In particular, an epoxy group can be mentioned as a preferable reactive group since it maintains or improves heat resistance and interlayer adhesive strength.

In order to obtain a prepreg from the above polyimide resin composition, after impregnating the base material with the above polyimide resin composition, the allyl group which is a reactive diluent with the polyimide resin is mixed with the polyimide resin while drying and evaporating the diluting solvent. It is obtained by semi-curing the resin composition in the base material by proceeding with the reaction with the BPA derivative contained in the base material. Furthermore, the reactive brominated resin contained in order to obtain flame retardancy reacts with the side chains and terminal groups of the polyimide resin during the preparation of this prepreg, and is incorporated into the skeleton of the polyimide resin structure. .

[0024] The type of substrate impregnated with the polyimide resin composition is not particularly limited. Usually, glass cloth or the like is used. In addition, inorganic fiber cloths such as quartz fiber cloths, nonwoven fabrics thereof, and highly heat-resistant organic fiber cloths such as polyimide resin fiber cloths and nonwoven fabrics can be used.

[0025] The temperature during semi-curing is 110 to 155
Preferably, it is carried out at °C. If the temperature exceeds 155 °C, the reaction of BPA derivatives having allyl groups will proceed too much, the interlayer adhesion of the obtained prepreg will decrease, and the effect of lowering the dielectric constant will be reduced. This is because it is not practical. Semi-cured refers to the range generally referred to as the B stage in the curing process of thermosetting resins, and refers to a state in which the resin flows when heat is applied and a curing reaction can occur.

Next, a polyimide resin laminate can be made by laminating one or more of the polyimide resin prepregs described above. That is, it is made by laminating and molding a prepreg with a metal foil such as copper, nickel, or aluminum, or a metal foil with a circuit formed thereon, as necessary. The lamination molding can be performed by a conventional method.

[0027] This laminate uses a polyimide resin composition in which a BPA derivative having an allyl group is blended with a polyimide resin having the above chemical structure, and the resin composition is sufficiently filled into the base material. It is being done. Therefore, by using this laminate, it is possible to obtain a laminate with a low dielectric constant and extremely high throughhole reliability. It is possible to obtain a laminate using a polyimide resin composition blended with a brominated resin having a brominated resin having interlaminar adhesion strength, through-hole reliability, heat resistance, and flame retardancy. , multilayer laminates, especially multilayer laminates with eight or more layers, have useful properties.

The resin composition of the present invention is not limited to the above description, but can also be used as a resin for covering electric wires, a resin for semiconductor encapsulation, a resin for heat-resistant molding materials, a low dielectric constant or low moisture absorption molding material, etc. It is also useful as a material resin.

Next, the above invention will be explained with reference to Examples and Comparative Examples.

[0030]

[Example] Examples 1 to 20 and Comparative Examples 1 and 2 were made of polyimide resin compositions having the respective formulations shown in the upper half of Table 1, and the characteristic values of laminates made of these resin compositions are shown below. 1
Shown in the bottom half of .

The following polyimide resins in Table 1 were used. #1 is synthesized from maleic acid N,N-4.4-diphenylmethane-bis-imide and 4.4-diaminodiphenylmethane, and does not contain an alkyl group or an alkylene group in the resin molecule. #2 is
It is synthesized from 1,4-bis(2-p-anilinopropylidene)benzene-bis-imide and 1,4-bis(2-m-anilinopropylidene)benzene, and the alkyl group is added to the resin. Contains 17% by weight in the molecule.

The derivative of BPA having an allyl group is BP
As the allyl ether of A, BPA-A manufactured by Mitsui Toatsu Co., Ltd.
E, dielectric constant 2.5, diallylbisphenol A
As a similar product, BPA-CA manufactured by Mitsui Toatsu Co., Ltd. has a dielectric constant of 3.7.
Each of these was used.

The brominated resins used as flame retardants are the ones indicated by (1) and (2) in Chemical Formula 1 at the end of the specification, respectively, and the types are specified with (■) before the compounding amounts in Tables 1 and 2. ■ is a reactive brominated phenol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., B
REN-S)■ is a non-reactive polycyclic aromatic brominated resin (manufactured by Gray Lake Co., Ltd., BC58), and the accelerator is
Both are 2ethyl-4methylimidazole (2E4M
Z, manufactured by Shikoku Kasei Co., Ltd.), and DMF was used as the diluting solvent so that the resin solid content was about 55 to 70%.

Examples 1 to 20 in Tables 1 and 2, Comparative Example 1,
From the comparison of the dielectric constant values of No. 2, it was confirmed that the dielectric constant decreases when a BPA derivative having an allyl group is blended into the polyimide resin.

Further, #1 polyimide resin of Examples 1 to 3, Examples 6 to 8, Examples 10 to 14, and Examples 16 to 18 and #1 of Examples 4, 5, 9, 15, 19, and 20 were added. From a comparison of the chemical structures of polyimide resin No. 2, it was confirmed that in the case of No. 2 containing 11% by weight or more of alkyl groups in the resin molecule, the dielectric constant was further reduced. The dielectric constant was measured according to JIS C6481.

[0036] Also, Examples 6 to 10, 14, 15, 18
The formulation of the reactive brominated resin having 20 reactive groups maintained a high level of interlayer adhesion and heat resistance compared to the formulation of the non-reactive brominated resin having no reactive groups in Example 11. It was confirmed that flame retardancy could be ensured. This flame retardancy test was conducted according to UL-94.

Next, the resin compositions shown in Tables 1 and 2 were applied to a thickness of 0.
1 mm, 95 g/m2 E glass cloth was impregnated with 1
Each prepreg was obtained by drying in a dryer at 40°C for 35 to 60 minutes. A laminate was formed using this prepreg in the following manner.

[0038] A double-sided roughened copper foil of 18 μm was placed on both sides of the prepreg, and a steam press was used to heat the molding temperature to 1.
30℃, molding pressure 30kg/cm2, molding time 90
A double-sided copper-clad laminate for an inner layer printed wiring board was obtained by lamination molding under conditions of 1 minute. The copper foil of the double-sided copper-clad laminate thus obtained was etched to form a circuit and blackened to create an inner layer printed wiring board, and 35 inner layer printed wiring boards were placed between each of the above-mentioned inner layer printed wiring boards. The same 4 sheets of prepreg as above are layered, and 35 μm thick copper foil is layered above and below through 4 sheets of prepreg, and 6 mm thick.
5 kg/cm2 using a steam press.
While applying pressure, the mixture was immediately heated to 130°C and held for 20 minutes. After this, at a pressure of 30 kg/cm2,
After heating to 0°C and holding for 120 minutes, the mixture was cooled to room temperature while applying pressure to obtain a double-sided copper-clad multilayer laminate.

The adhesive strength when the layers of this laminate were peeled off in a 90 degree direction is shown in Tables 1 and 2 as interlayer adhesive strength [kg/cm] in the characteristic values. Also, this laminate has 0.4
Using a mmφ drill bit, 1,000 holes were drilled at a rotation speed of 40,000 rpm and a feed rate of 50 μ/rev per rotation, and through-hole plating was performed using a combination of electroless plating and electrolytic plating using a conventional method. 1
The cross-section of the 000th hole was observed with a microscope, and the plating penetration length and through-hole wall roughness, which occur during through-hole plating, were measured, and the results are shown in Tables 1 and 2. shown in the column of characteristic values. In addition, the examples in which BPA-AE or BPA-CA were blended were the same as those in the examples in which reactive flame retardants were blended. This is reduced compared to 1 and 2. However, in Example 11, in which a non-reactive brominated resin was blended to impart flame retardancy, flame retardance was obtained in the same manner as in Example 10, in which a reactive brominated resin was blended. Heat resistance decreases. Due to this decrease in heat resistance, the through-hole wall surface becomes rough and cracks occur due to the heat generated during drilling, and as a result, the through-hole plating penetration length and through-hole wall surface roughness are the same as in Comparative Example 1. The effect of blending the BPA derivative having an allyl group will be lost. By blending a reactive brominated resin, flame retardancy can be ensured without reducing heat resistance. This prevents the through-hole wall surface from becoming rough or cracking due to heat generated during drilling, and the through-hole plating penetration length and through-hole wall roughness are significantly reduced compared to comparative examples. .

The small characteristic values of the penetration length of the through hole plating and the roughness of the wall surface of the through hole both prevent deterioration of the insulation between the through hole plating and the inner layer circuit, and prevent the through hole plating from deteriorating. This improves reliability.

[0041]

Effects of the Invention: A laminate obtained by obtaining a prepreg using the polyimide resin composition of the present invention, laminating and curing the prepreg reduces the dielectric constant of the laminate, and increases the propagation speed of electric signals. It is suitable for use in a wide variety of applications, and has high through-hole reliability due to good filling properties of the resin into the base material, making it possible to create a single-layer multilayer laminate, and further improving safety due to its flame retardancy.

[0042]

[Chemical formula 1]

[0043]

[Table 1]

[0044]

[Table 2]

Claims (15)

[Claims] 1) 1) polyimide resin; 2) bisphenol having an allyl group, which is blended in an amount ranging from 10 to 200 parts by weight based on 100 parts by weight of the polyimide resin;
3) A polyimide resin composition comprising a derivative of Le A, 3), an accelerator, a solvent, and the like. 2. The polyimide resin of claim 1 is a polyimide resin prepared by reacting an unsaturated bis-imide with a diamine, and wherein at least one of an alkyl group or an alkylene group other than a methylene group is added to the polyimide resin. The polyimide resin composition according to claim 1, wherein the polyimide resin composition contains at least % by weight. 3. Claim 1, wherein the derivative of bisphenol A having an allyl group according to claim 1 is an allyl ether of bisphenol A or a diallylbisphenol A class. The polyimide resin composition described. 4. The polyimide resin composition according to claim 1 is blended with a brominated resin having a reactive group in an amount of 1 to 50 parts by weight of bromine based on 100 parts by weight of the polyimide resin. The polyimide resin composition according to claim 1. 5. The polyimide resin composition according to claim 1, wherein the brominated resin having a reactive group according to claim 4 is a brominated epoxy resin. 6. 1) polyimide resin; 2) bisphenol having an allyl group, which is blended in an amount ranging from 10 to 200 parts by weight per 100 parts by weight of the polyimide resin;
1. A polyimide resin prepreg characterized in that a base material is impregnated with a polyimide resin composition comprising a derivative of Le A, 3), an accelerator, a solvent, etc., and semi-cured. 7. The polyimide resin of claim 6 is a polyimide resin prepared by reacting an unsaturated bis-imide with a diamine, and wherein at least one of an alkyl group or an alkylene group other than a methylene group is added to the polyimide resin. The polyimide resin prepreg according to claim 6, characterized in that the polyimide resin prepreg contains at least % by weight. 8. Claim 6, wherein the derivative of bisphenol A having an allyl group according to claim 6 is an allyl ether of bisphenol A or a diallylbisphenol A class. Prepreg of the polyimide resin described. 9. The polyimide resin composition according to claim 6 is blended with a brominated resin having a reactive group in an amount of 1 to 50 parts by weight of bromine based on 100 parts by weight of the polyimide resin. The polyimide resin prepreg according to claim 6. 10. The polyimide resin prepreg according to claim 6, wherein the brominated resin having a reactive group according to claim 9 is a brominated epoxy resin. 11. 1) a polyimide resin, 2) a derivative of bisphenol A having an allyl group, which is blended in an amount ranging from 10 to 200 parts by weight per 100 parts by weight of the polyimide resin, 3), and A polyimide resin laminate, characterized in that a base material is impregnated with a polyimide resin composition comprising an accelerator, a solvent, etc., and one or more semi-cured prepregs are laminated and cured. 12. The polyimide resin of claim 11 is a polyimide resin prepared by reacting an unsaturated bis-imide with diamide, wherein at least one of an alkyl group or an alkylene group other than a methylene group is added to the polyimide resin.
12. The polyimide resin laminate according to claim 11, wherein the polyimide resin contains at least % by weight. 13. Claim 11, wherein the derivative of bisphenol A having an allyl group according to claim 11 is an allyl ether of bisphenol A or a diallylbisphenol A class. A laminate of the polyimide resin described above. 14. The polyimide resin composition according to claim 11 is blended with a brominated resin having a reactive group in an amount of 1 to 50 parts by weight based on bromine content based on 100 parts by weight of the polyimide resin. A laminate of polyimide resin. 15. The polyimide resin laminate according to claim 11, wherein the brominated resin having a reactive group according to claim 14 is a brominated epoxy resin.