JPH0480261A - Polyimide resin composition, its prepreg and its laminate - Google Patents

Abstract

PURPOSE:To obtain a polyimide resin composition which is excellent in the infiltrability of resin into a substrate and is useful for obtaining a laminate excellent in through-hole reliability by mixing a polyimide resin with a specified triallyl isocyanurate and an accelerator, a diluent, etc. CONSTITUTION:This composition is prepared by mixing a polyimide resin (e.g. a resin comprising maleic acid N,N'-4,4'-diphenylmethane-bisimide and 4,4'- diaminodiphenylmethane), with 10-200pts.wt., per 100pts.wt. above resin, triallyl isocyanurate prepared by mixing 50-90pts.wt. triallyl isocyanurate monomer with 50-10pts.wt. trimethallyl isocyanurate, an accelerator (e.g. 2-ethyl-4- methylimidazole), a diluent (e.g. DMF), etc.

Description

Detailed Description of the Invention [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 obtained by curing this prepreg. This invention relates to resin laminates.

[Conventional technology]

Conventionally, polyimide resins and epoxy resins have been widely used as resins for laminated boards and the like. Among them, polyimide resins are disclosed in JP-A-59-20659 and JP-A-61-4.
As described in Japanese Patent No. 0322, it has been widely used in high-multilayer wiring boards for high-density packaging.

The reason for this lies in the following important characteristics. ■High-precision processing such as miniaturization of wiring conductors and micro-hole drilling is possible in order to increase the density of wiring boards.■The coefficient of thermal expansion in the thickness direction is low, and the through-hole plating provides high conductivity characteristics.■ However, in recent years, polyimide Resin laminates are designed to accommodate the increasing speed of semiconductors in line with the increasing speed of electromechanical devices that use semiconductor devices to hold computers, to increase the propagation speed of electrical signals, and to enable high-density packaging of -layers. There was a strong desire to improve reliability through multi-layering, as well as improve safety.

[Problem to be solved by the invention]

The present inventors have addressed these issues by first reducing the permittivity of the laminate to accommodate the higher propagation speed of electrical signals, and improving the resin base material to improve through-hole reliability. The present invention provides a polyimide resin composition, a prepreg thereof, and a laminate thereof, which enable high-density packaging due to its filling properties, and further improve safety due to flame retardancy.

Accordingly, it is an object of the present invention to further provide a polyimide resin composition, a prepreg thereof, and a laminate thereof, which stably exhibit these properties of low dielectric constant and high through-hole conductivity due to good filling properties of the resin into a base material. It is in.

[Means to solve the problem]

The present invention has been made in view of the above points. As a result of research into reducing the dielectric constant of commonly known addition type polyimide resins, the present inventors have found that We found an effective chemical structure and its quantitative contribution. In addition, it has been found that when a predetermined amount of triallylisocyanurate is blended, the dielectric constant further decreases. When using triallyl isocyanurate ff, a homogeneous and stable prepreg can be obtained by using the triallyl isocyanurate monomer in combination with a predetermined amount of trimethallyl isocyanurate, which has excellent through hole conductivity and has low dielectric properties. They have discovered a polyimide resin composition and a prepreg thereof that can stably produce a laminate with a high density.

Furthermore, by blending a predetermined amount of a brominated resin having a reactive group, it is possible to stably obtain a flame-retardant, low dielectric constant laminate without causing side effects such as a decrease in adhesion and heat resistance. They have discovered a polyimide resin composition and its prepreg that can be used.

The polyimide resin composition includes (a) polyimide resin, and (b) 10 to 10 parts by weight of the polyimide resin.
Triallylisocyanurates are blended in an amount ranging from 200 parts by weight, and these triallylisocyanurates include 50 to 90 parts by weight of triallylisocyanurate and 50 to 10 parts by weight of trimethallyl isocyanurate. (c), an accelerator, a diluting solvent, etc. In addition, in order to obtain flame retardance, the bromine content is added to 100 parts by weight of the polyimide resin. So 1~
It is characterized in that it is made by blending a brominated resin having a reactive group in the range of 50 parts by weight.6 In addition, the polyimide resin prepreg includes (a) a polyimide resin, and (b) 100 parts by weight of the polyimide resin. 10~
Triallyl isocyanurate is blended in an amount ranging from 200 parts by weight, and the triallyl isocyanurate contains 50 to 90 parts of triallyl isocyanurate monomer.
parts by weight, and trimethallyl isocyanurate is 50 to 10
It is characterized by impregnating a base material with a resin composition for laminates consisting of a mixture of parts by weight (c), an accelerator, a diluting solvent, etc., and semi-curing it, and further In order to obtain flame retardancy, the bromine content should be 1 to 100 parts by weight of polyimide resin.
It is characterized by containing 50 parts by weight of a brominated resin having a reactive group.

In addition, the polyimide resin laminate is made of (a) polyimide resin (b) 10 to 10 parts by weight of the polyimide resin (b)
Triallylisocyanurates are blended in an amount ranging from 200 parts by weight, and these triallylisocyanurates include 50 to 90 parts by weight of triallylisocyanurate and 50 to 10 parts by weight of trimethallyl isocyanurate. It is characterized by curing a prepreg prepared by impregnating a base material with a resin composition for laminates consisting of an accelerator, a diluting solvent, etc. and semi-curing it, Furthermore, in order to obtain flame retardancy, a brominated resin having a reactive group in a range of 1 to 50 parts by weight of bromine is blended with 100 parts by weight of the polyimide resin. .

These will be explained in detail below.

Polyimide resins can be obtained by reacting unsaturated bis-imides with diamines and the like. The polyimide resin obtained in this way preferably contains at least 11% by weight of at least one of an alkyl group or an alkylene group other than a methylene group, because the polyimide resin contains at least 11% by weight of an alkyl group or an alkylene group other than a methylene group. If the group has a chemical structure of less than 11% by weight in the resin molecule,
This is because the dielectric constant of polyimide resin cannot be lowered.

The unsaturated bis-imide may be represented by the following formula (I), and the diamine may be represented by the following formula (n).

[The formula (I) represents a divalent group containing a carbon-carbon double bond, and A represents a divalent group containing at least 2 carbon atoms.] H, N-B-NH, (It) [B in formula (II) has 30 or less carbon atoms 2
A of formula (1) and B of formula (II) can be the same or different and are straight-chain or branched alkylene groups having less than 13 carbon atoms. or 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. can. These various groups may have substituents that do not cause unnecessary side reactions under reaction conditions of reaction temperature of 70 to 170 DEG C. and reaction time of 30 to 350 minutes.

A in formula (1) and B in formula (II) can also represent a number of phenylene groups or an alicyclic group bonded directly or with divalent atoms or groups such as . For example, they are oxygen or sulfur, or one carbon atom
from 3 to 3 alkylene groups, or one of the following groups:
It is one.

NR4--P (0)R,-,-N=NO=N--Co
-0-, -3o.

S i Rz R4, C0NH NY-Co-X-Co-NY -o-co-x-co-o- In the formula, R8 and Y each have 1 to 4 carbon atoms, and as many as 5 alkyl groups in the ring. represents a cyclic alkyl group having 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, 5 in the ring or a cyclic alkylene group having 6 carbon atoms, or a monocyclic or polycyclic arylene group.

The following formula including the group in formula (1) above is derived from an ethylene anhydride, such as maleic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, itaconic anhydride. , and can also represent the product of a Diels-Alder reaction between a cyclodiene and one of these anhydrides.

Preferred unsaturated bis- of formula (1) that can be used
Imides include the following:

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
・41 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・N1-methaxylylene 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-bisimide, 1,4-
Bis(2-m-anilinopropylidene)benzene-bis-imide, 4,4'methylene-2,6-xylysine-
Bis-imide, 4,4'-methylene di-2,6-ethylaniline-bis-imide, 4,4°-diamino-3,
3゜-Diethyl-5,51-dimethyldiphenylmethane-bis-imide, 4,41-methylenedi-2,6-diitupropylaniline-bis-imide, 2,5-dimethyl-p-phenylenediamine-bis-imide, 2. 2-bis(4-aminophenyl)propane-bis-imide, 2
・4-diaminomesitylene-bis-imide, and 3
- 5-diethyl-2,4-tolylenediamine-bis-imide, etc.

Examples of diamines of formula (It) that can also be used include: 4・4゛-diaminodicyclohexylmethane, ■・4-diaminocyclohexane, 2・
6-diamitupyridine, metaphenynediamine, paraphenynediamine, 4,4'-diaminodiphenylmethane, 2,2-bis-(4-aminophenyl)propane, henzidine, 4,4'-diaminophenyl oxide, 4
・41 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-bis-(para-aminophenyl)phthalane, hexamethylene diamine,
anilinopropylidene)benzene, 1,4-bis(2-
p-anilinopropylidene)benzene, 1,4-bis(
2-m-anilinopropylidene)benzene, 4.4°-
Methylenedi2,6-xylidine, 4,41-methylenedi2,6-diethylaniline, 4,41-diamino3,
31-diethyl-5,5'-dimethyldiphenylmethane, 4,41-methylenedi-2,6-diisoprobylaniline, 2,5-dimethyl-p-phenylenediamine, 2.
2-bis(4-aminophenyl)propane, 2,4-diaminomesitylene, and 3,5-diethyl-2,4
- Tolylene diamine etc.

Then, an addition type polyimide resin can be prepared by reacting the above bis-imide with a diamine. The mixing ratio of bis-imide and diamine is preferably in a molar ratio of 1.7 to 2.5 bis-imide to 1 diamine. If the amount of bis-imide is less than 17, a large amount of high molecular weight will be produced, shortening the curing time, and there will be problems in handling.If the amount of bis-imide is more than 2.5, a large amount of unreacted raw material will remain. It becomes Shimasa. The reaction is bis-
Imide and diamine are combined into N-methylpyrrolidone (NMP).
or N,N-dimethylacetamide (DMAc).
The heating temperature during the reaction can be in the range of about 70 to 170°C, and the reaction time can be in the range of about 30 to 350 minutes.

The polyimide resin composition of the present invention contains 10 to 20 parts by weight of the above-mentioned polyimide resin and triallyl isocyanurate (hereinafter referred to as TAIC).
TAIC of this TAIC class in an amount within the range of 0 parts by weight.
Trimethallylisocyanurate (hereinafter referred to as TMAIC) is blended in a range of 50 to 10 parts by weight to 50 to 90 parts by weight of the monomer, and further, imidazoles, organic peroxides, etc. are added as accelerators. As a diluting solvent, DMAc, dioxane, NMPSMEK, dimethylformamide (DMF), etc., may be used alone or as appropriate.
It is a resin composition consisting of mixed materials. TAI
CI! As the amount of addition 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 decreases. However, the laminate becomes hard and brittle, which is undesirable.Additionally, the addition of TA I C monomer and TMAI C lowers the intrinsic viscosity and surface tension of the resin composition, which causes the resin composition to deteriorate between the fibers of the base material. The material penetrated well, and the volatilization of TAIC monomer during the drying process was suppressed due to TMA I C, and the remaining amount of TAIC was stabilized and increased. A significantly improved prepreg can be stably obtained. In the laminated board in which this C prepreg is cured, the penetration length of the through-hole plating is significantly shortened without any variation, and at the same time, the inner wall of the through-hole is finished extremely smooth and without any variation. The insulation properties were ensured, and through-hole reliability was stabilized and significantly improved.

The amount of TAIC monomer and TMA I C used is TAr
c Nanatsuma - TMAIC50~90 parts by weight
It is blended in an amount of 10 parts by weight, and this range of blending can suppress the intense volatilization of the TAIC monomer during drying during prepreg production. TAIC
This effect is observed when TMAIC is added to the monomer when TMAICIO is added, and the effect is no longer changed even if more than 50 parts are added, so it is limited to the above range. As a result, the resin composition impregnated into the base material can be semi-cured in a sufficiently stable manner, and a prepreg in which the resin filling into the base material is significantly improved can be stably obtained.

In order to ensure the flame retardancy required for the safety of electronic mechanical devices, it is necessary to incorporate a brominated resin having a reactive group as a flame retardant into the polyimide resin composition. The blending amount of polyimide resin is 100%
It is necessary to use it in a range of 1 to 50 parts by weight based on the bromine content. The reason is that less than 1 part by weight,
This is because flame retardancy cannot be obtained, and if more than 50 parts by weight is used, the heat resistance of the resulting laminate deteriorates, the dielectric constant increases, and performance deteriorates. 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.

Therefore, as a reactive group, an alkyl having 1 to 4 carbon atoms having an epoxy group, an allyl group, a vinyl group, etc.
cyclic alkyl or phenyl or polycyclic aromatic with 5 or 6 carbon atoms in the ring, or 1
from among brominated resins such as straight-chain or branched alkylenes having less than 3 carbon atoms, cyclic alkylenes having 5 or 6 carbon atoms in the ring, or monocyclic or polycyclic arylenes; It 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,
Polyimide resin and TAIC while drying the diluted solvent once
It is obtained by semi-curing the resin composition in the base material by proceeding with the reaction with monomers and TMA IC. 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 W of the base material to be impregnated with the polyimide resin composition is not particularly limited, and glass cloth or the like is usually used. In addition, inorganic fiber cloth such as quartz fiber cloth, highly heat-resistant organic fiber cloth such as polyimide resin fiber cloth, etc. may be used.

The temperature during semi-curing is preferably 110 to 155°C. If the temperature exceeds 155°C, the TAIC monomer in particular will easily volatilize, the reaction will proceed too much, the interlayer adhesion of the resulting prepreg will decrease, and the effect of lowering the dielectric constant will become smaller. 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 above-mentioned polyimide resin prepregs. That is, if necessary, a metal foil such as copper, nickel, or aluminum or a circuit formed thereon can be made. It is made by laminating prepreg and metal foil. The lamination molding can be performed by a conventional method.

Note that this laminate uses a polyimide resin composition in which TA I CII is blended with a polyimide resin having the above chemical structure, and the resin composition is stably and sufficiently filled into the base material. . Therefore, by using this laminate, it is possible to obtain a laminate that stably has the characteristics of low dielectric constant and extremely high through hole reliability, and this T
A laminate using a polyimide resin composition in which a brominated resin having a reactive group is further blended into a polyimide resin composition containing AI CM has excellent interlayer adhesion, sulfur resistance, heat resistance, and flame retardancy. It becomes possible to obtain a laminate having both properties, and multilayer laminates, particularly multilayer laminates with eight or more layers, have useful properties. Next, the above invention will be explained using Examples and Comparative Examples.

〔Example〕

Examples 1 to 18 and Comparative Examples 1 to 3 are made of polyimide resin compositions having the respective formulations shown in the upper half of Tables 1 and 2, and the characteristics of prepregs and laminates made of these resin compositions are as follows. The values are shown in the lower half of Tables 1 and 2.

The following polyimide resins were used in Tables 1 and 2, respectively.

H is synthesized from maleic acid N, N'-4,4'-diphenylmethane-bis-imide and 4,41-diaminodiphenylmethane, and does not contain an alkyl group or an alkylene group in the resin molecule.

Cloud 2 is 4,4'-methylenedi2,6-xylysine-
It is synthesized from bis-imide and 4,4'-diaminodiphenylmethane, and has one alkyl group in the resin molecule.
Contains 3% by weight.

Cloud 3 was synthesized from 4,4'-methylenedi-2,6-dinithylaniline-bis-imide and 1,4-bis(2-panilinopropylidene)benzene, and the alkyl group was added to the resin molecule. Contains 24.5%.

s4 is 4,4'-methylene-2,6-diisopropylaniline-bis-imide and 1,4-bis(2-P-7-
1-! J-nopropylidene) benzene, and contains 30% by weight of alkyl groups in the resin molecule.

I5 is synthesized from 1,4-bis(2-P-anilinopropylidene)benzene-bis-imide and 1,4-bis(2-m-anilinopropylidene)benzene, and has an alkyl group. is contained in the resin molecule in an amount of 17% by weight.

The following brominated resins are used as flame retardants.
In Tables 2 and 2, the types are clearly indicated with ■ to ■ before the compounding amounts.

■: Reactive brominated phenol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., BR[!N-5); ■: Reactive brominated bisphenol A epoxy resin (manufactured by Tobu Kasei Co., Ltd., YDB-400) (2) is a non-reactive polycyclic aromatic brominated resin (manufactured by Great Lake Co., Ltd., BC58) (2) is a non-reactive polycyclic aromatic brominated resin (manufactured by Great Lake Co., Ltd., BC52) Brominated resins as flame retardants are, respectively,
It is represented by the following chemical structural formula.

■ 2 to 4 ■ In addition, 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Co., Ltd.) was used as the accelerator, and DMF was used as the diluent so that the resin solid content was approximately 60%. there was.

Examples 1-18, Comparative Example 2 and Comparative Example 1 in Tables 1 and 2
From the comparison of the characteristic value of dielectric constant with polyimide resin, TA
I C1t, i.e., TAIC monomer or TMA r
TII that when C is blended, the induction rate decreases! I could recognize it.

Furthermore, from the comparison of the chemical structures of the polyimide resins of Examples 1 to 5 and Examples 7 to 13 and the polyimide resins of Examples 6 and 14 to 18, it was found that an alkyl group was added to the resin molecule with 11
It was confirmed that when the content is more than % by weight, there is an effect of lowering the -layer dielectric constant. This dielectric constant measurement is carried out by JIS
, C6481.

In addition, in the formulation of reactive brominated resins having reactive groups in Examples 7 to 11 and Examples 14 to 18, Examples 12 and 13
It was confirmed that flame retardancy can be ensured while maintaining interlayer adhesion and heat resistance at a high level compared to formulations of non-reactive brominated resins that do not have reactive groups. This flame retardant test is UL-
It was carried out according to 94.

Next, polyimide resin prepreg will be explained.

Other than Example 18 in Table 1, the trees BFi in Tables 1 and 2 are
Each prepreg was obtained by impregnating a 0.1 m thick, 95 g/ax" E glass cloth with &I acid and drying it in a dryer at 140°C for 40 minutes. In Example 18,
A prepreg was similarly obtained using a D glass cloth with a thickness of 0.1 mm and a thickness of 105 gems instead of the E glass cloth.

As a result, as shown in the prepreg volatile content [wt%] of the characteristic values in Tables 1 and 2, when only the TAIC monomer of Comparative Example 2 was used, the volatilization during the drying process was severe and the semi-curing of the resin was stabilized. In addition, the resulting prepreg has a large volatile content, which causes bulges and voids in laminates using this prepreg. In contrast, Example 1
TMAI f
In the case of C, the vapor pressure is TMA I CO, 24 mHg/1
34°C, TA I C/7-3mHg/144°C
Compared to using TAIC monomer alone, the boiling point of TAIC monomer increases by using TMA I C in combination, so the volatilization of TAIC monomer during the drying process is reduced, and the remaining amount of TAIC becomes stable and increases. It is thought that the reduction in the rate will further progress.

In addition, the prepreg volatile content is the prepreg weight before drying W1
The prepreg weight W2 after drying at 180°C for 30 minutes was measured and calculated from the formula 100X (Wl-W2)/W1.

Next, an example of a laminate formed using the prepreg described above will be described.

A double-sided roughened copper foil of 18 μm was placed on both sides of the prepreg, and laminated molding was performed using a steam press at a molding temperature of 13°C and a molding pressure of 30 kg/cm for 90 minutes to form an inner layer printed wiring board. A double-sided copper-clad laminate was obtained. Inner layer printed wiring boards were created by etching the copper foil of the double-sided copper-clad laminate obtained in this way to form a circuit, and 35 inner layer printed wiring boards were placed between each of the 4 same inner layer printed wiring boards. 35 μ-thick copper foil was layered on top and bottom of the prepreg with another 4 sheets of prepreg placed between them, placed in a 6an mold, and pressurized to 5 kg/cm using a steam press. Immediately heated to 130°C and held for 20 minutes. After this, 30kg/cm"
The sample was heated to 200° C. under a pressure of 200° C., held for 120 minutes, and then cooled to room temperature while keeping the pressure applied to obtain a double-sided copper-clad multilayer laminate.

The adhesion force when the layers of this laminate are peeled off in a 90° direction is calculated as the interlayer adhesion force [kg/cm'
Shown in J. In addition, 1,000 holes were drilled in this laminate using a drill bit with a diameter of 0.4 m under the conditions of 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 conventional method using electroless plating and electrolytic plating. The cross section of the 990 to 1000-sized through holes was observed with a microscope, and the penetration length of the through holes that occurred during through hole plating and the roughness of the wall surface of the through holes were measured. Table 1, 2
It is shown in the characteristic value column of the table.

In Examples 1 to 6, in which TA I C monomer and TMA I C were blended, and in Examples 7 to 11, and Examples 14 to 18, in which reactive flame retardant side was further blended, throughhole plating was The penetration length is reduced compared to Comparative Example 1. Furthermore, compared to Comparative Example 2, the difference between the maximum value and the average value of the plating penetration length of the through holes was smaller, so it was confirmed that the obtained properties were stable. However, in Examples 12 and 13, in which non-reactive brominated resin was blended in the same amount as the reactive brominated resin, flame retardancy could not be obtained. heat resistance decreases. Due to this decrease in heat resistance,
As a result of heat generation during drilling, the through-hole wall surface becomes rough and cracks occur, and as a result, the plating penetration length of the through-hole and the wall surface roughness of the through-hole are worse than in Comparative Example 1.
The effect of the combination of ICs will be lost.

However, as mentioned above, in the formulation of reactive brominated resin,
It ensures flame retardancy and does not reduce heat resistance. Therefore, it prevents the wall surface of the through hole from becoming rough or cranking due to the heat generated during drilling, so the length of penetration of the plating of the through hole also reduces the roughness of the wall surface of the through hole. This is also significantly reduced compared to Comparative Example I, and compared to Comparative Example 2, the difference between the length of plating penetration of the through holes and the maximum value and average value of the wall surface roughness of the through holes is smaller, so the obtained properties are stable. I was able to confirm something.

The small characteristic values of the penetration length of the through-hole plating and the wall surface roughness of the through-hole both prevent the insulation between the through-hole plating and the inner layer circuit from deteriorating and improve the through-hole continuity. . In addition, compared to Example 17, Example 18 only changed the base material to D glass cloth.
Although it is true that the dielectric constant can be reduced by the contribution of D glass, disadvantages appear such as the length of plating penetration of the through holes becomes longer and the roughness of the through hole walls becomes rougher due to the hardness of the base material.

〔Effect 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 is stable and suitable for increasing the propagation speed of electric signals. It enables higher-density packaging due to its high through-hole reliability due to stable and good filling properties into the resin base material, and also improves safety due to its flame retardancy.

Patent applicant Matsushita Electric Works Co., Ltd.

Claims (12)

[Claims] (1) (a) Polyimide resin, (b) 10 to 10 parts by weight of the polyimide resin
Triallyl isocyanurate is blended in an amount ranging from 200 parts by weight, and the triallyl isocyanurate contains 50 to 90 parts of triallyl isocyanurate monomer.
parts by weight, and trimethallyl isocyanurate is 50 to 10
A polyimide resin composition comprising (c) an accelerator, a diluting solvent, etc., blended in the following parts by weight. (2) The polyimide resin is made of steel by reacting unsaturated bis-imide and diamine, and the polyimide resin contains at least 11% by weight of at least one of an alkyl group and an alkylene group other than a methylene group. The polyimide resin composition according to claim 1, characterized in that: (3) A brominated resin having a reactive group having a bromine content in the range of 1 to 50 parts by weight based on 100 parts by weight of the polyimide resin is blended into the polyimide resin composition according to claim 1. Polyimide resin composition. (4) The polyimide resin composition according to claim 3, wherein the brominated resin having a reactive group is a brominated epoxy resin. (5) (a) Polyimide resin (b) 10 to 100 parts by weight of the polyimide resin
Triallyl isocyanurate is blended in an amount ranging from 200 parts by weight, and the triallyl isocyanurate contains 50 to 90 parts of triallyl isocyanurate monomer.
parts by weight, and trimethallyl isocyanurate is 50 to 10
A prepreg of a polyimide resin, characterized in that a base material is impregnated with a polyimide resin composition consisting of (c), an accelerator, a diluent solvent, etc. blended in a range of parts by weight, and semi-cured. (6) The polyimide resin is a polyimide resin prepared by reacting an unsaturated bis-imide with a diamine, and the polyimide resin contains at least 11% by weight of at least one of an alkyl group and an alkylene group other than a methylene group. The polyimide resin prepreg according to claim 5, characterized in that: (7) The polyimide resin composition according to claim 5 is characterized by blending a brominated resin having a reactive group in a range of 1 to 50 parts by weight in terms of bromine content based on 100 parts by weight of the polyimide resin. Polyimide resin prepreg. (8) The polyimide resin prepreg according to claim 7, wherein the brominated resin having a reactive group is a brominated epoxy resin. (9) (a) Polyimide resin, (b) 10 to 10 parts by weight of the polyimide resin
Triallyl isocyanurate is blended in an amount ranging from 200 parts by weight, and the triallyl isocyanurate contains 50 to 90 parts of triallyl isocyanurate monomer.
parts by weight, and trimethallyl isocyanurate is 50 to 10
A base material is impregnated with a polyimide resin composition consisting of a polyimide resin composition containing a mixture of parts by weight (c), an accelerator, a diluent solvent, etc., and one or more semi-cured prepregs are laminated and cured. Characteristic polyimide resin laminate. (10) The polyimide resin is made of steel by reacting unsaturated bis-imide and diamine, and the polyimide resin contains at least 11% by weight of at least one of an alkyl group or an alkylene group other than a methylene group. The polyimide resin laminate according to claim 9, characterized in that: (11) The polyimide resin composition according to claim 9 has a bromine content of 1 to 50 parts by weight based on 100 parts by weight of the polyimide resin.
1. A polyimide resin laminate comprising a brominated resin having reactive groups in the range of parts by weight. (12) The polyimide resin laminate according to claim 11, wherein the brominated resin having a reactive group is a brominated epoxy resin.