JP3372982B2 - Thermosetting resin composition and prepreg and laminate using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin material having excellent heat resistance, low hygroscopicity and adhesiveness. In particular,
The present invention relates to a resin material useful as a laminated board for a printed wiring board and the like, and a laminated board using the resin material.

[0002]

2. Description of the Related Art With regard to printed wiring boards widely used in electric / electronic devices, communication devices, computing devices, etc., the wiring density has become more sophisticated and highly integrated.
There is an increasing demand for improved reliability by improving the heat resistance of laminated wiring boards. BACKGROUND ART Conventionally, epoxy resins, unsaturated polyester resins, polyimide resins, phenol resins, etc. have been used as resin materials for forming laminated boards for printed wiring boards. Of these resins, epoxy resins and bismaleimides have been used. The polyamino bismaleimide resin obtained by reacting a diamine with an aromatic diamine is widely used for high-density packaging and high-multilayer laminates.

[0003]

However, although the epoxy resin has relatively good heat resistance, it meets the recent demand for higher heat resistance due to high density mounting of printed wiring boards and high multilayer structure. Inevitably, there is a limit to the increase in heat resistance. Further, in the case of a polyamino bismaleimide resin, although its heat resistance is very excellent, it has high hygroscopicity and has a difficulty in adhesion, and it is necessary to use a high boiling point solvent such as dimethylformamide when forming a varnish. Therefore, the residual solvent is increased in the prepreg, and voids are easily generated during lamination. Furthermore, there is a problem in that the cost becomes high because higher temperature and longer time are required for stacking than the epoxy resin. Further, in order to compensate for the drawbacks of this polyamino bismaleimide resin, there is an imide-modified epoxy resin obtained by adding an epoxy resin to a polyamino bismaleimide resin, but this resin also requires a high boiling point solvent, and the residual solvent in the prepreg is There are many problems,
Further, there is a problem that the heat resistance is significantly inferior to that of the polyamino bismaleimide resin.

For this reason, it is possible to cope with future progress in high-density mounting and multi-layering, has excellent heat resistance, has low hygroscopicity, and has excellent performance such as adhesiveness, and voids are less likely to occur during lamination. There has been a strong demand for resin materials for laminated boards at low cost. The present invention has been made in view of such circumstances, eliminates the drawbacks of conventional epoxy resins and polyimide resins, is excellent in heat resistance, and is a new resin for laminates that can satisfy other properties as well. The purpose is to provide the material.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that polymaleimide resin is an epoxy resin having a naphthalene skeleton, a phenol resin having a naphthalene skeleton, and one molecule. O inside
It is modified with a compound having an H group and an epoxy group and having a molecular weight of 300 or less, is soluble in general-purpose solvents such as methyl ethyl ketone, and has excellent heat resistance and low hygroscopicity due to the introduction of a naphthalene skeleton into epoxy resin and phenol resin. And a thermosetting resin composition mainly composed of a modified imide resin, which is characterized by excellent adhesiveness. The present invention also provides a prepreg in which a base material is impregnated with this resin composition, and a thermosetting resin laminated plate characterized by being formed by laminating a plurality of prepregs.

As the polymaleimide compound used in the present invention, any compound having two or more maleimide groups in one molecule can be used. Examples of such a polymaleimide compound include N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N '.
-(1,3-phenylene) bismaleimide, N, N '-[1,3- (2-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, bis (4- Maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-
Maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,
4-bis (4-maleimidophenyl) cyclohexane, 1,4-
Bis (maleimidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3 -Maleimidophenoxy)
Phenyl] methane, bis [4- (4-maleimidophenoxy)
Phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3 -Maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [ Four
-(4-maleimidophenoxy) phenyl] propane, 2,2-
Bis [4- (3-maleimidophenoxy) phenyl] butane,
2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl
Le] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4
-(4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4'-bis (3-maleimidophenoxy) biphenyl, 4,4'-bis (4-maleimide Phenoxy) biphenyl, bis [4- (3-maleimidophenoxy)
Phenyl] ketone, bis [4- (4-maleimidophenoxy)
Phenyl] ketone, bis [4- (3-maleimidophenoxy)
Phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-
Maleimidophenoxy) phenyl] sulfone, bis [4-
(4-Maleimidophenoxy) phenyl] sulfone, bis
[4- (3-maleimidophenoxy) phenyl] ether,
Bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimide) Phenoxy) -α, α-dimethylbenzyl] benzene, 1,
4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4- Screw
[4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-
Dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy)-
3,5-Dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, general formula (2) (Chemical formula 2)

[0007]

[Chemical 2] (In the formula, n is 0 to 10 on average), and a polymaleimide compound represented by the general formula (3)

[0008]

[Chemical 3] (In the formula, m is an average value of 0 to 10) and the like. These polymaleimide compounds may be used alone or in combination of two or more.

As the epoxy resin of the component (a) used in the present invention, any epoxy resin having at least two epoxy groups in one molecule and having at least one naphthalene skeleton can be used. These are illustrated below. From a novolak resin which is a reaction product of naphthols such as naphthol and dihydroxynaphthalene and naphthols or phenols such as phenol, cresol and resorcinol, and aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, gluoxal and alkanedial. Derived novolak type epoxy resins and aralkyl type epoxy resins derived from aralkyl resins which are reaction products of the above naphthols, phenols and aralkyl alcohol derivatives. In addition, an epoxy resin derived from a compound having two or more active hydrogens and a naphthalene skeleton in one molecule, for example, an epoxy resin obtained by reacting dihydroxynaphthalene, diaminonaphthalene and the like with epichlorohydrin or 2-methylepichlorohydrin One or two or more of these epoxy resins are used.

As the component (b), any phenol resin having at least two OH groups in the molecule and having at least one naphthalene skeleton can be used. These are illustrated below. Naphthols such as naphthol and dihydroxynaphthalene and naphthols or phenols such as phenol, cresol and resorcinol and formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde,
Examples include novolak resins, which are reaction products with aldehydes such as gluoxal and alkanedials, and aralkyl resins, which are reaction products with naphthols, phenols and aralkyl alcohol derivatives. One of these phenolic resins or Two types are used.

As the component (c), glycidol, glycerin diglycidyl ether, ethylene glycol monoglycidyl ether, resorcinol monoglycidyl ether, naphthresorcinol monoglycidyl ether, etc., one alcoholic or phenolic OH group in one molecule, , Molecular weight 3 containing one or more epoxy groups
Examples of the compounds are 00 or less. Even if it is a compound containing one alcoholic or phenolic OH group and one or more epoxy group in one molecule, if the molecular weight is 300 or more, it produces a modified imide resin soluble in a general-purpose solvent such as methyl ethyl ketone. You cannot do it.

The above polymaleimide resin, (a),
The components (b) and (c) at the same time at 100 to 200 ° C.,
Generally, the mixture is heated and mixed for 0.1 to 10 hours, but with respect to the polymaleimide resin, the component (c) alone causes gelation by heating for a short time (for example, 130 ° C., 10 minutes), The production of stable modified imide resins is difficult. On the other hand, when the components (a) and (c) are added to the polymaleimide resin and mixed by heating, the modified imide resin can be stably produced without gelation even when heated for a long time. Further, for the polymaleimide resin, (a)
When components (b) and (c) are added and mixed by heating, (a)
The target modified imide resin can be produced in a shorter time than when the component (c) is added.

The component (c) is preferably used in an amount of 5 to 100 parts by weight with respect to 100 parts by weight of the polymaleimide resin. In particular, for the purpose of maintaining heat resistance and solubility in a general-purpose solvent such as methyl ethyl ketone, it is 15 parts by weight. It is preferable to use ˜50 parts by weight.

The epoxy resin as the component (a) is generally 10 to 50 parts by weight with respect to 100 parts by weight of the polymaleimide resin.
Although 0 part by weight is used, 20 to 200 parts by weight is preferable for the purpose of stability during production and heat resistance.

The amount of the phenol resin as the component (b) is in the range of 1 to 500 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the epoxy resin of the component (a). The resin composition of the present invention contains the modified imide resin as a main component, and if necessary, a cresol novolac type epoxy, a bisphenol type epoxy-free epoxy which does not include a naphthalene skeleton, and / or a phenol novolac. Resin, phenol resin not containing naphthalene skeleton such as phenol aralkyl resin, amines typified by diaminodiphenylmethane, diaminodiphenyl sulfone, dicyandiamide, etc., and acid anhydrides such as phthalic anhydride, pyromellitic dianhydride, etc. may be used in combination. .

In the present invention, when curing the resin composition, it is desirable to include a curing accelerator,
As such a curing accelerator, 2-methylimidazole,
Imidazoles such as 2-methyl-4-ethylimidazole and 2-heptadecylimidazole; amines such as triethanolamine, triethylenediamine and N-methylmorpholine; organic phosphines such as tributylphosphine, triphenylphosphine and tritolylphosphine ;
Tetraphenylphosphonium tetraphenylborate,
And tetraphenylboron salts such as triethylammonium tetraphenylborate; 1,8-diaza-bicyclo (5,4,0) undecene-7 and its derivatives. These curing accelerators may be used alone or in combination of two or more, and if necessary, an organic peroxide or an azo compound may be used in combination. The content of these curing accelerators is 0.01 to 10 with respect to 100 parts by weight of the resin.
Used in the range of parts by weight.

In addition to the above-mentioned various components, the resin material of the present invention has a reactivity that is generally used for imide resins such as diallyl phthalate, triallyl isocyanurate and o, o'-diallyl bisphenol A, if necessary. Diluents; various silicone oils; flame retardants such as bromine compounds, antimony and phosphorus; fillers; other suitable additives may be added. When the resin composition of the present invention as described above is used as a resin material for laminates, the resin is dissolved in a solvent to form a resin varnish, the base material is impregnated and dried, and a prepreg is prepared. A predetermined laminated plate can be obtained by pressurizing and laminating and integrating.

As the base material, a suitable material such as glass mat, glass sheet, non-woven fabric, paper or the like can be used, and in lamination molding, a metal foil of copper, aluminum, stainless steel or the like is placed on the outermost layer, and molding is carried out. It can be a laminate for wiring boards. You may use it as a laminated board for multilayer printed wiring boards using an inner layer core material.

[0019]

EXAMPLES The present invention will be specifically described below with reference to examples. The test method of the performance in the examples is as follows.・ Volatile content: JIS C-6487 ・ Glass transition temperature: Dynamic viscoelasticity method ・ Copper foil peel test: JIS C-6482 ・
Water absorption rate: JIS C-6481, Solder heat resistance: JIS
According to C-6481, after boiling the test piece for 1 hour, 300
It was dipped in a solder bath at ℃ for 120 seconds, and the presence or absence of abnormality of the laminated plate was examined.

The following raw materials were used as the raw materials used in the examples and comparative examples.・ Polymaleimide compound; bis (4-maleimidophenyl) methane (manufactured by Mitsui Toatsu Chemicals, Inc.) ・ Epoxy resin; naphthalene-containing epoxy resin (EOCN-7)
000, manufactured by Nippon Kayaku Co., Ltd.

[0021]

[Chemical 4] ・ Epoxy resin; naphthalene-containing epoxy resin (EPICLO
N-4032, manufactured by Dainippon Ink and Chemicals, Inc.

[0022]

[Chemical 5] -Epoxy resin; o-cresol novolac type epoxy resin (EOCN-1020, manufactured by Nippon Kayaku Co., Ltd.)-Epoxy resin: Bisphenol A type epoxy resin (Epicoat 1001, manufactured by Yuka Shell Epoxy Co., Ltd.)-Phenol resin; Naphthalene-containing phenolic resin (OC
N-7000, manufactured by Nippon Kayaku Co., Ltd.

[0023]

[Chemical 6] -Phenol resin; Naphthol ziloc resin (NX, manufactured by Mitsui Toatsu Chemicals, Inc.)

[0024]

[Chemical 7] -Phenolic resin; novolac type phenolic resin (PN-8
0, manufactured by Nippon Kayaku Co., Ltd.-Glycidol; Epiol OH (manufactured by NOF CORPORATION) -Curing accelerator: 2 ethyl 4-methyl imidazole (2E4MZ)
, Shikoku Kasei Co., Ltd. ・ Polyamino bismaleimide resin; Kelimide 601A (Rhone Poulenc Company)

Examples 1 to 4 and Comparative Examples 1 to 6 (Production of modified imide resins A to J ) A reactor equipped with a stirrer, a thermometer and a cooler has the compositions of A to J in Table 1. Thus, the raw materials were inserted and reacted at 130 ° C. for 30 minutes or 1 hour to obtain modified imide resins AJ.

[0026] 100 parts by weight of methyl ethyl ketone added to modified imide resin A to J 100 parts by weight (solubility in methyl ethyl ketone), was examined solubility in methyl ethyl ketone-modified imide resin A to J at room temperature. The results are shown in Table 1.

As shown in Examples 1 to 4 and Comparative Examples 1 and 2, when the polymaleimide resin, the epoxy resin, the phenol resin, and the component (c) have a proper composition, 13
A modified imide resin soluble in methyl ethyl ketone can be obtained by heating at 0 ° C. for 30 minutes.

Comparative Example 5 is a case where the phenol resin is not used during the modification, but a precipitate is formed when the heating time is 30 minutes. Therefore, it is understood that the intended modified imide resin can be obtained in a short time by using the phenol resin. Further, as shown in Comparative Examples 3, 4, and 6, when the polymaleimide resin, the epoxy resin, the phenol resin, and the component (c) are not modified with an appropriate composition, the modified imide resin obtained does not gel during modification. It can be seen that precipitation occurs. Furthermore, since the epoxy resin Epicoat 1001 used in Comparative Example 6 is a compound containing one OH group and two epoxy groups in one molecule, it has a molecular weight of 900, and therefore it precipitates when dissolved in methyl ethyl ketone. A thing arises.

Examples 5 to 8 and Comparative Examples 7 to 11 The modified imides prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were dissolved in a flask with the composition (parts by weight) shown in Table 2. A thermosetting resin composition varnish was obtained. Since polyamino bismaleimide resin is insoluble in methyl ethyl ketone, dimethylformamide was used as the solvent. The modified imide resin varnish thus obtained was treated with 104
A glass cloth of g / m ² was impregnated and dried at 140 ° C. for 5 minutes to obtain a prepreg of about 190 g / m ² . Five sheets of this prepreg were stacked, copper foil was placed on the upper and lower outermost layers, and the pressure was 40 kg / cm ² at 170 ° C. and 60 ° C.
Molding was performed under heating conditions for a minute to obtain a copper clad laminate having a thickness of 0.5 mm.

Table 2 shows the test results of the obtained prepreg and laminated plate. For comparison, a modified imide resin E containing no naphthalene skeleton in the phenol resin (Comparative Example 7 ) and a modified imide resin containing no naphthalene skeleton in the epoxy resin
F (Comparative Example 8 ), polyamino bismaleimide resin (Comparative Example 9 ), mixed resin of polyamino bismaleimide resin and epoxy resin having naphthalene skeleton and phenol resin having naphthalene skeleton (Comparative Example 10 ), and epoxy resin (Comparative Example) Also for 11 ), a prepreg and a laminated board were manufactured, and the resin characteristics thereof were evaluated in the same manner. In addition,
In the case of the polyamino bismaleimide resin of Comparative Example 9, 20
It was molded under heating conditions of 0 ° C. and 120 minutes.

Compared with Examples 5 to 8 of the present invention, in the case of the polyamino bismaleimide resin, the volatile content in the prepreg is large. In Comparative Examples 7 and 8, since the epoxy resin or the phenol resin does not contain a naphthalene skeleton, the water absorption rate is higher and the solder heat resistance is inferior to the Examples. As described above, the levels were not satisfied with all of the hygroscopicity, the adhesiveness, and the solder heat resistance as compared with the present example.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

As described in Examples and Comparative Examples, the thermosetting resin composition according to the present invention is soluble in a general-purpose solvent such as methyl ethyl ketone, has a low volatile content in the prepreg, and is excellent in workability. By introducing a naphthalene skeleton into epoxy resin and phenol resin, it is a new thermosetting resin composition that has high Tg, low hygroscopicity, good adhesiveness, and excellent solder heat resistance. It is an effective material.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08L 63/00 C08L 63/00 (72) Inventor Kotaro Asahina 1190 Kasamacho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (56) Reference Documents JP-A 5-112630 (JP, A) JP-A 6-145299 (JP, A) JP-A 63-86758 (JP, A) JP-A 4-328120 (JP, A) JP-A 4- 328119 (JP, A) JP-A-6-233486 (JP, A) JP-A-58-125717 (JP, A) JP-A-58-65718 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/40-59/66 B32B 15/08 C08G 59/24 C08J 5/24 C08L 63/00-63/10

Claims (5)

(57) [Claims] 1. A polymaleimide resin represented by the general formula (1) (Chemical Formula 1): (In the formula, R ₁ is a monovalent organic group, Xa and Xb are hydrogen atoms,
Same or different monovalent atom or group selected from halogen atom and organic group, l is an integer of 2 or more),
An epoxy resin having at least two or more epoxy groups in the molecule and having at least one naphthalene skeleton, and (b) a phenol having at least two or more OH groups in the molecule and having at least one naphthalene skeleton. A modified imide resin obtained by modifying a resin and (c) a compound having a molecular weight of 300 or less and having one alcoholic or phenolic OH group and one or more epoxy groups in the molecule , (c) The amount of compounds in the polymer
5 to 100 parts by weight based on 100 parts by weight of the reimide resin,
The amount of the epoxy resin (a) is polymaleimide resin 1
10 to 500 parts by weight per 100 parts by weight of the component (b)
100 parts by weight of epoxy resin of component (a)
On the other hand, a thermosetting resin composition containing 1 to 500 parts by weight of a modified imide resin as a main component. 2. The thermosetting resin composition according to claim 1, which comprises a curing accelerator, a flame retardant, a filler and the like. 3. A prepreg comprising a base material impregnated with the resin material according to claim 1. 4. A thermosetting resin laminate comprising a plurality of the prepregs according to claim 3 laminated. 5. The thermosetting resin laminate according to claim 4, which is integrally formed with the outermost metal foil.