JPH04222863A - 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, a triallyl isocyanurate, 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. total amounts of B1: a triallyl isocyanurate (including polymer) and B2: an allyl group-containing bisphenol A derivative, preferably 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), prepreg and a laminate thereof. 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 heretofore been widely used as resins for laminated boards and the like. Among them, polyimide resins are disclosed in Japanese Patent Application Laid-Open No. 59-20659,
As described in Japanese Unexamined Patent Publication No. 61-40322, it has been widely used in high multilayer wiring boards for high-density packaging.

Particularly in recent years, efforts have been made to reduce the dielectric constant of polyimide resin laminates in order to accommodate the increased propagation speed of electrical signals in electronic and mechanical devices using semiconductor devices, including computers. It was expected to ensure good impregnation of the resin into the base material in order to improve throughhole reliability, prevent penetration of throughhole plating, and improve safety due to flame retardancy. As a technique corresponding to these, the present inventors previously disclosed Japanese Patent Application No. 1-333456.

[0004] However, as through-holes are becoming more and more multi-layered, in order to further improve the reliability of through-holes, while maintaining a low dielectric constant for increasing the propagation speed of electrical signals and flame resistance for safety, through-holes have been developed. There has been a strong desire to further reduce the penetration of plating solutions and prevent the occurrence of through-hole cracks.

[0005]

[Problem to be solved by the invention]Thus, while maintaining a low dielectric constant for increasing the propagation speed of electrical signals and flame resistance for safety, through-holes have become even more reliable as multi-layering continues to progress. An object of the present invention is to provide a polyimide resin composition, a prepreg thereof, and a laminate thereof, which can further reduce the penetration of a through-hole plating solution and prevent the occurrence of through-hole cracks in order to improve the properties of the polyimide resin composition.

[0006]

[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 triallylisocyanurates and a derivative of bisphenol A having an allyl group are blended, the dielectric constant is further reduced. In addition, when triallylisocyanurates or derivatives of bisphenol A having an allyl group are used, the intrinsic viscosity of the resin decreases, a homogeneous and stable prepreg can be obtained, and it has excellent throughhole reliability. They have discovered a polyimide resin composition and its prepreg that can produce a laminate with a low dielectric constant. Furthermore, by blending a predetermined amount of brominated resin with reactive groups,
We have discovered a polyimide resin composition and prepreg thereof that can produce a laminate that has flame retardancy, low dielectric constant, and excellent through-hole reliability without causing side effects such as decreased adhesion and heat resistance. It is.

The polyimide resin composition comprises: 1) a polyimide resin; 2) triallylisocyanurate compounded in a total amount in the range of 10 to 200 parts by weight based on 100 parts by weight of the polyimide resin; It is characterized by consisting of a derivative of bisphenol A having an allyl group, 3), an accelerator, a solvent, etc. Furthermore, in order to obtain flame retardancy, bromine is added to 100 parts by weight of the polyimide resin. It is characterized by containing a brominated resin having a reactive group in a content range of 1 to 50 parts by weight.

[0008] Furthermore, polyimide resin prepreg has 1
) polyimide resin, 2) a derivative of bisphenol A having triallyl isocyanurate and an allyl group, which are blended in a total amount of 10 to 200 parts by weight based on 100 parts by weight of the polyimide resin. , 3) and is characterized in that the base material is impregnated with a polyimide resin composition consisting of an accelerator, a solvent, etc. and semi-cured. It is characterized by containing a brominated resin having a reactive group in an amount of 1 to 50 parts by weight based on the weight of bromine.

[0009] Furthermore, the polyimide resin laminate includes 1) a polyimide resin, and 2) triallyl isocyanurate, which is blended in a total amount in the range of 10 to 200 parts by weight based on 100 parts by weight of the polyimide resin. a derivative of bisphenol A having a group and an allyl group, 3) and an accelerator;
It is characterized by laminating and curing one or more semi-cured prepregs in which a base material is impregnated with a polyimide resin composition consisting of a solvent etc. Furthermore, in order to obtain flame retardancy, It is characterized in that it contains a brominated resin having a reactive group in an amount of 1 to 50 parts by weight based on bromine content per 100 parts by weight of the polyimide resin.

[0010] 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 (
In b), B in formula (b) can be represented by a divalent group having 30 or less carbon atoms.

H2 NB-NH2
(b) Note that A in formula (a) and B in formula (b) can be the same or different and are straight-chain or branched alkylene groups having fewer than 13 carbon atoms. , a cyclic alkylene group having 5 or 6 carbon atoms in the ring, a heterocyclic group containing at least one of O, N and S atoms, or a phenylene or polycyclic aromatic group. . These various groups have a reaction temperature of 70 to 170°C and a reaction time of 30 to 35°C.
It may have a substituent that does not cause unnecessary side reactions under the reaction conditions of 0 minutes.

Note that A in formula (a) and B in formula (b)
also has many phenylene groups or directly or two
It can also represent a valence atom or an alicyclic group bonded by the following groups. For example, they are oxygen or sulfur, the group of alkylenes 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 chemical formulas, R3, R4 and Y each represent an alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms in the ring, or phenyl or a polycyclic aromatic group, 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 in the ring, 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,
It can also represent tetrahydrophthalic 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.

The polyimide resin composition of the present invention contains 100 parts by weight (hereinafter referred to as parts) of the polyimide resin, triallylisocyanurate (hereinafter referred to as TAIC), and bisphenol A having an allyl group. (hereinafter referred to as BPA) in a total amount in the range of 10 to 200 parts by weight, and further contains imidazoles and organic peroxides as accelerators, and dimethylformamide (hereinafter referred to as BPA) as a diluting solvent. DMF), DMAc, dioxane, NMP,
It is a resin composition consisting of MEK and the like, used alone or in combination. When the amount of TAICs and BPA derivatives having an allyl group added is increased, the dielectric constant of the resulting laminate tends to decrease, and if the total amount of these is less than 10 parts, the effect of decreasing the dielectric constant is It is hardly observed, and if it exceeds 200 parts, the dielectric constant decreases, but the laminate becomes hard and brittle, which is not preferable. In addition, TAIC types include TAIC polymer and TAIC
It is a general term for The amount of TAIC polymer and TAIC used is 0 to 10 parts by weight per 1 part by weight of TAIC polymer.
Preferably, the amount is 0 parts by weight. These reasons are below. That is, regarding the amount of TAIC and its polymer used, the TAIC polymer also includes a TAIC prepolymer, and the addition of the TAIC polymer can suppress the intense volatilization of TAIC during drying during prepreg production. This allows the resin composition impregnated into the base material to be semi-cured in a sufficiently stable manner, making it possible to obtain a prepreg in which the resin filling of the base material is significantly improved. TAIC polymer and TAI
When using C, the effect can be achieved even if the addition amount is as small as 1 part by weight per 100 parts by weight of the polyimide resin, and the effect can be achieved even if only TAIC polymer is used.

[0021] The weight average molecular weight of the TAIC polymer is preferably 500 to 10,000, especially 500 to 10,000.
00 to 3000 polymers are preferred. This is because, in the case of a polymer with a weight average molecular weight of less than 500, the above TA
The effect of IC polymer cannot be obtained, and the weight average molecular weight is 100.
If a polymer exceeding 0.00 is used, the plasticity of the resin composition decreases, the interlayer adhesion of the prepreg becomes weak, and the laminate becomes hard and brittle. This stuff is sulfo-
Cracks occur on the inner wall of the through hole during hole processing. As a result, the plating solution permeates during through-hole plating, resulting in poor insulation between the through-holes and the inner layer circuit, which is undesirable as it reduces the reliability of the through-holes. In addition, T.A.
The weight average molecular weight of the IC polymer is a value determined based on a monomer calibration curve using a GPC chart.

Therefore, TAI used to lower the dielectric constant.
BPA with an allyl group can be used to prevent through-hole cracks that occur when using Class C without interfering with the low dielectric constant.
We have discovered that it is possible to use derivatives of TAIC in combination with TAICs. A derivative of BPA having an allyl group is
It has the same reactivity and reaction mechanism as TAICs, and can be copolymerized with polyimide resin, TAICs, etc., and has interlayer adhesive strength,
This method reduces the overall crosslink density of the polyimide resin composition and improves the crack resistance of the resin against external stress without impairing properties such as heat resistance, water resistance, and electrical insulation contact.

[0023] Furthermore, bisphenol A having an allyl group
Derivatives include 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 preferred because they are liquid and easy to use in varnishes, and their volatility is suitable for manufacturing conditions.

[0024] TAICs and allyl group-containing BPA derivatives also act as reaction diluents and reduce 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 a laminate made of hardened prepreg, there is almost no through-hole cracking during through-hole drilling, the penetration length of the through-hole plating is significantly shortened, and at the same time, the inner walls of the through-holes are extremely smooth. As a result, the insulation between the through hole and the inner layer circuit is ensured, and the reliability of the through hole is significantly improved.

In order to ensure the flame retardancy required for the safety of electronic mechanical devices, it is preferable 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 a bromine content is 1 to 5 by weight based on 100 parts by weight of the polyimide resin.
It is preferable to use it in a range of 0 parts by weight. The reason is 1.
If the amount is less than 50 parts by weight, flame retardancy cannot be obtained, and if the amount exceeds 50 parts by weight, the heat resistance of the resulting laminate will be poor and the dielectric constant will also increase, resulting in decreased performance. Furthermore, brominated resins having reactive groups are preferable because the flame retardant is reacted with the side chains and terminal groups of the polyimide resin, and is incorporated into the skeleton of the polyimide resin structure. This is because it is possible to obtain a product that combines reliability, heat resistance, and flame retardant performance.

[0026] 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 diluent is dried and evaporated while the polyimide resin is mixed with a reactive diluent such as TAIC or the like. It is obtained by semi-curing the resin composition in the base material by proceeding with the reaction with a BPA derivative having an allyl group. 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. .

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 may be used.

[0029] 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 TAICs and allyl group-containing BPA derivatives will proceed too much, and the interlayer adhesion of the resulting prepreg will decrease.
This is because the effect of lowering the dielectric constant becomes small, and if the temperature is lower than 110° C., the processing takes time and 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.

[0031] This laminate includes a polyimide resin having the above chemical structure, TAICs, and BP having an allyl group.
A polyimide resin composition containing a derivative of A and the like is used, and the base material is sufficiently filled with the resin composition. Therefore, by using this prepreg, it is possible to obtain a laminate with particularly high through-hole reliability, which has a low dielectric constant, can further reduce through-hole plating penetration, and can prevent the occurrence of through-hole cracks.
In a laminate using a polyimide resin composition in which a BPA derivative having group C and an allyl group is further blended with a brominated resin having a reactive group, high sulfol reliability and layer It becomes possible to obtain a laminate that has both interlayer adhesive strength, heat resistance, and flame retardancy, and multilayer laminates, especially multilayer laminates with eight or more layers, have useful properties.

[0032] The resin composition of the present invention is not limited to the above description, and may also be used as a resin for coating electric wires, a resin for semiconductor encapsulation, a resin for heat-resistant molding materials, a resin with a low dielectric constant, and a low moisture absorption. It is also useful as a resin for molding materials.

Next, the above invention will be explained using examples and comparative examples.

[0034]

[Example] Examples 1 to 8 and Comparative Examples 1 to 3 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. It is shown in the lower half of 1.

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.

TAIC is manufactured by Nippon Kasei Co., Ltd. and has a dielectric constant of 2.
．． 9, the allyl group-containing BPA derivative 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 those represented by (1) and (2) in Chemical Formula 1 at the end of the specification, respectively, and the types are specified with (■) in front of the blending amounts in Table 1. ■ is a reactive brominated phenol.
Lunovolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., BREN
-S) ■ is a non-reactive polycyclic aromatic brominated resin (manufactured by Gray Lake Co., Ltd., BC58), and the accelerator is 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Co., Ltd.). The diluting solvent has a resin solids content of about 55~
DMF was used in each case to give a concentration of 70%.

From the comparison of the dielectric constant characteristic values of Examples 1 to 8 and Comparative Examples 1 to 3 in Table 1, BPA, which is a derivative of BPA having an allyl group, was found in the resin composition of polyimide resin and TAIC.
It was confirmed that even when -AE or BPA-CA was added or alternatively blended, a low dielectric constant was maintained or further reduced.

Furthermore, from a comparison of the chemical structures of #1 polyimide resin of Examples 1 and 2 and #2 polyimide resin of Examples 3 to 8, #1 containing an alkyl group in the resin molecule in an amount of 11% by weight or more was found. In the case of No. 2, it was confirmed that the dielectric constant was further reduced. This dielectric constant measurement is based on JIS, C6
It was done by 481.

In addition, in the formulation of the reactive brominated resin having a reactive group in Examples 2 and 4 to 8, the formulation of the non-reactive brominated resin without a reactive group in Examples 1 and 3 was In comparison, it was confirmed that flame retardancy could be ensured while maintaining interlayer adhesion and heat resistance at a high level. This flame retardant test is UL-9
It was carried out according to 4.

Next, the resin composition shown in Table 1 was applied to a thickness of 0.1 m.
m, 95 g/m2 E glass cloth impregnated, 140
Each prepreg was obtained by drying for 35 to 60 minutes in a dryer at .degree. A laminate was formed using this prepreg in the following manner.

[0042] 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
Lamination molding was carried out under conditions of 1 minute to obtain a double-sided copper-clad laminate for an inner layer printed wiring board. 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 45 inner layer printed wiring boards were placed between each of the above 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.
Place it in a mold of 5 kg/cm using a steam press.
Immediately heat to 130 °C while applying pressure in step 2.
It was held for 0 minutes. Thereafter, it was heated to 200° C. under a pressure of 30 kg/cm 2 and held for 120 minutes, and then cooled to room temperature while the pressure was applied to obtain a double-sided copper-clad multilayer laminate.

The adhesive force when the layers of this laminate are peeled off in a 90 degree direction is determined by the interlayer adhesive force [k] of the characteristic values in Table 1.
g/cm]. Also, 0.4 mm on this laminate
Using a φ drill bit, the rotation speed is 40,000 rpm, and the feed rate per rotation is 50 μ/rev.
00 holes were drilled and throughhole plating was performed using a combination of electroless plating and electrolytic plating using a conventional method, and the cross section of the throughholes at holes 990 to 1000 was observed with a microscope to determine the throughholes produced during throughhole plating. The plating penetration length was measured, and the results are shown in the characteristic value column of Table 1.

[0044]Through-hole cracks occur in this laminate at a rate of 0.
Using a 3 mmφ drill bit, holes were drilled at a rotation speed of 80,000 rpm and a feed rate of 10 μ/rev per rotation, and 30 through holes (500 to 529 holes) were observed with a microscope to determine the number of cracks larger than 30 μm. were evaluated, and the results are shown in the column of characteristic values in Table 1.

Furthermore, in any of Examples 2 and 4 to 8 in which a reactive flame retardant was blended, the length of throughhole plating penetration and the number of occurrences of throughhole cracks were improved by blending a non-reactive brominated resin. This is reduced compared to Example 3. When imparting flame retardance, non-reactive brominated resins can provide the same flame retardancy as reactive brominated resins, but the heat resistance is reduced. 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 penetration length of the through-hole plating becomes worse. The effect of the combination of derivatives will be lost. However, by blending a reactive brominated resin, flame retardancy can be ensured and heat resistance will not be reduced. Therefore, cracks do not occur due to heat generated during drilling, and the roughness of the through-hole wall surface and the length of plating penetration into the through-hole are significantly reduced.

[0046]

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 compatible with the above, and enables higher through-hole reliability by reducing penetration of through-hole plating solution and preventing the formation of through-holes, and further improves safety through flame retardancy. It is.

[0047]

[Chemical formula 1]

[0048]

[Table 1]

Claims (15)

[Claims] 1. 1) a polyimide resin, 2) a triallylisocyanurate compound blended in a total amount of 10 to 200 parts by weight with respect to 100 parts by weight of the polyimide resin, and an allyl group. A polyimide resin composition comprising a bisphenol A derivative, 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) a polyimide resin, 2) a triallylisocyanurate compound blended in a total amount of 10 to 200 parts by weight with respect to 100 parts by weight of the polyimide resin, and an allyl group. A polyimide resin prepreg characterized in that a base material is impregnated with a polyimide resin composition comprising a bisphenol A derivative, 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 total amount of 10 to 200 parts by weight based on 100 parts by weight of the polyimide resin;
A base material is impregnated with a polyimide resin composition consisting of triallyl isocyanurates, a derivative of bisphenol A having an allyl group, 3), an accelerator, a solvent, etc., blended in an amount within the range of parts by weight. 1. A polyimide resin laminate, characterized in that 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. The polyimide resin laminate according to claim 11. 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.