JPH05140305A - Fluorine-containing biscyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition excellent in moldability, heat resistance as well as adhesion and low in dielectric constant and free from producing by-product by blending a specific bismaleimide compound with a biscyanamide compound. CONSTITUTION:The objective resin composition is obtained by blending (A) a bismaleimide compound expressed by formula I [R is H, alkyl or halogen; (n) is 1-4] with (B) a discyanamide compound expressed by formula II (C9F17 group is perfluorononenyl group having one double bond; X is divalent group containing ester bond or ether bond). The components A and B are used at a blend ratio of (95:5) to (5:95). Further, the biscyanamide compound can be blended with a maleimide compound, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing thermosetting resin composition, and more particularly to a resin composition suitable as a low dielectric constant insulating material excellent in moldability, heat resistance and adhesiveness.

[0002]

2. Description of the Related Art Bismaleimide has been conventionally used as a heat-resistant thermosetting resin composition, but it has been found that a resin obtained by adding bismaleamide to bismaleimide has improved heat resistance and moldability. Issued (JP-A-58-71)
No. 924 publication). However, it is known that these resins have a relatively high relative dielectric constant because they have a large number of amide groups or imide groups having a large polarizability. As a thermosetting resin composition having a low relative dielectric constant, a resin using a fluorine-containing maleimide or the like has been proposed (JP-A-2-73809), but it is known that the introduction of fluorine reduces the adhesiveness. Has been.
Therefore, a material having both adhesiveness and low relative permittivity is required for use in a multilayer printed board of a large-sized computer that requires high-speed signal transmission.

[0003]

In the conventional thermosetting resin composition, a fluorine-substituted functional group was introduced as a means for lowering the relative dielectric constant, but this method impairs the adhesiveness to a metal. There is a drawback that In general, it is known that a polar functional group such as an ester may be introduced to improve the adhesiveness, but in a usual method, the relative dielectric constant becomes high.

An object of the present invention is to provide a resin composition which has a low relative dielectric constant without impairing heat resistance and adhesiveness and does not generate a by-product during molding which is a characteristic of imide-based materials. is there.

[0005]

The present invention will be described in brief. By combining a functional group having a polarity with a fluorine-containing maleimide compound and a fluorine-containing cyanamide compound that can compensate for an increase in the relative dielectric constant due to the introduction thereof, heat resistance can be improved. It is possible to provide a resin composition which has a low relative dielectric constant without impairing adhesiveness and does not generate a by-product at the time of molding, which is a feature of imide-based materials.

Claim 1 General formula (1)

[0007]

[Chemical 11]

(Wherein R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4), and a bismaleimide compound represented by the general formula (2)

[0009]

[Chemical 12]

(Wherein, C ₉ F ₁₇ group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond). A thermosetting resin composition comprising a compound.

(2) A mixing ratio of the bismaleimide compound of (1) and the biscyanamide compound of (1) is 95: 5.
A thermosetting resin composition, characterized in that it is used at 5:95. Claim 3 General formula (1)

[0012]

[Chemical 13]

(Wherein R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4), and a bismaleimide compound represented by the general formula (2)

[0014]

[Chemical 14]

(In the formula, the C ₉ F ₁₇ group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.) A thermosetting resin composition comprising a cyanamide compound and at least one of a maleimide compound, a cyanamide compound, a cyanato compound, an isocyanato compound, an epoxy compound and a vinyl compound.

4. A resin composition prepared by dissolving the resin composition in a solvent according to claim 1, 2 or 3 and using a uniform varnish.

Claim 5 General formula (1)

[0018]

[Chemical 15]

(Wherein R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4), and a bismaleimide compound represented by the general formula (2)

[0020]

[Chemical 16]

(Wherein C ₉ F ₁₇ is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond). A method for producing a cured resin product, which comprises using a compound to obtain a three-dimensional crosslinked cured product by a polymerization reaction of multiple bonds.

6. A method for producing a cured resin product according to claim 5, wherein the polymerization reaction of multiple bonds is heat polymerization.

7. A method for producing a cured resin product according to claim 5, wherein the polymerization reaction of multiple bonds is polymerization in the presence of an anionic polymerization initiator such as an alkoxy compound.

8. A method for producing a cured resin product according to claim 5, wherein the polymerization reaction of the multiple bonds is polymerization in the presence of a radical polymerization initiator such as peroxide.

9. A method for producing a cured resin product according to claim 5, wherein the polymerization reaction of multiple bonds is photopolymerization such as UV irradiation.

Claim 10 General formula (1)

[0027]

[Chemical 17]

(Wherein R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4), and a bismaleimide compound represented by the general formula (2)

[0029]

[Chemical 18]

(Wherein, C ₉ F ₁₇ group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond). A cured product obtained by three-dimensionally crosslinking a resin composition containing a compound by a polymerization reaction of multiple bonds.

11. A cured resin product according to claim 10, wherein the polymerization reaction of the multiple bonds is heat polymerization.

12. A cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is polymerization in the presence of an anionic polymerization initiator such as an alkoxy compound.

13. A cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is polymerization in the presence of a radical polymerization initiator such as peroxide.

14. A cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is photopolymerization such as UV irradiation.

15. A cured product according to claim 10, which has a relative dielectric constant of 3 or less.

Claim 16 General formula (1)

[0037]

[Chemical 19]

(Wherein R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4), and a bismaleimide compound represented by the general formula (2)

[0039]

[Chemical 20]

(Wherein, C ₉ F ₁₇ group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond). An electrical insulator using a cured product obtained by three-dimensionally crosslinking a resin composition containing a compound by a polymerization reaction of multiple bonds.

(17) A prepreg obtained by impregnating an inorganic fiber cloth, which is a reinforcing material, with the resin composition according to (1), (2), (3) or (4).

18. A prepreg obtained by impregnating an organic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4.

(19) A laminated material using the resin composition according to (1), (2), (3) or (4).

20. A laminate material using the resin composition according to claim 1, 2, 3 or 4 together with other resin components.

21. A laminated material obtained by laminating and adhering a prepreg obtained by impregnating an inorganic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4.

22. A laminated material obtained by laminating and adhering a prepreg obtained by impregnating an organic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4.

[23] A wiring board comprising the resin composition according to any one of [1] to [22] and a laminated material using the composition.

24. A large area substrate comprising the resin composition according to any one of claims 1 to 22 and a laminated material using the composition.

25. A module substrate comprising the resin composition according to any one of claims 1 to 22 and a laminated material using the composition.

[26] A microchip carrier substrate comprising the resin composition according to any one of [1] to [22] and a laminated material using the composition.

(27) A pin grid array substrate formed of the resin composition according to any one of (1) to (22) and a laminated material using the composition.

In the present invention, examples of the fluorine-containing maleimide compound represented by the general formula (1) are shown below.

[0053]

[Chemical 21]

Further, the fluorine-containing cyanamide compound represented by the general formula (2) in the present invention includes, for example, those shown below.

[0055]

[Chemical formula 22]

However, examples of the C ₉ F ₁₇ group include those shown below.

[0057]

[Chemical formula 23]

Although these compounds have polar groups for improving the adhesiveness, the bond dissociation energy with carbon is 100 kJ / mol greater than that of hydrogen, and the content of fluorine having a large molar specific volume is large. Since it also has high substituents, it has excellent adhesiveness and heat resistance, and it has become possible to obtain thermosetting resins with a low dielectric constant.

By using these compounds as the composition of thermosetting resin, the moldability of the resin can be improved, and at the same time, since it has a fluorine-substituted substituent, the resin has excellent heat resistance and a low dielectric constant. I was able to get

A thermosetting resin using a fluorinated cyanamide compound and a fluorinated maleimide compound is resistant to heat due to the formation of a melamine ring which is a heteroaromatic ring or an isomer ring of an isomeramine ring and a complex three-dimensional cross-linking by a trimerization reaction such as heating. A low dielectric constant material with excellent properties. This results in a heat-resistant insulating material that retains mechanical properties and dimensional stability even at high temperatures. Further, since the reaction by-product such as condensed water is not generated in this crosslinking and curing reaction, there is an advantage that it can be applied in various fields such as various structural materials and molding. This is different from typical heat-resistant insulating materials such as polyimide, polybenzimidazole, and polybenzothiazole.

[0061]

The polar group introduced to improve the adhesiveness of the thermosetting resin raises the dielectric constant because the bond dissociation energy with carbon is 100 kJ / mol higher than that of hydrogen and the inclusion of fluorine with a large molar specific volume. It became possible by introducing a substituent with a high ratio. The heat resistance was able to maintain the conventional properties by retaining the maleimide and cyanamide structures that construct a three-dimensional cross-link by the polymerization reaction of multiple bonds.

[0062]

【Example】

<Example 1> 80 g of 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (A) (central glass)
-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-cyanamidephenoxy) phenyl)
(C) (Manac) 20 g with methyl isobutyl ketone 10
It was dissolved in 0 g and subjected to prepolymerization under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing conditions are 150 ° C., and once the sample is melted, 250
The temperature was raised to ° C and pressure was applied. The characteristics of the obtained resin plate were evaluated. The relative permittivity is LF manufactured by Hewlett Packard
Using the impedance analyzer 4192A, JIS-
The capacitance of the sample was measured according to C-6481 and the relative permittivity was calculated. Regarding the coefficient of thermal expansion, using a thermomechanical property measuring device TM-3000 manufactured by Vacuum Riko Co., Ltd., a resin plate of 7 mm x 7 mm
Expansion coefficient (50-220) in the thickness direction of the sample cut into
C) was measured. The measurement was performed in a compression mode with a temperature rising rate of 2 ° C./min and a load of 10 g. Bending strength was measured according to JIS-C-6481, using Autograph DDS-5000 manufactured by Shimadzu Corporation. A sample cut out from a resin plate into a size of 50 mm × 5 mm was measured under the conditions of a fulcrum distance of 30 mm and a bending speed of 2 mm / min. The thermal decomposition starting temperature was measured using a high speed differential thermal balance TGD-7000RH manufactured by Vacuum Riko. About 10 mg of a powder sample obtained by crushing a resin component, a heating rate of 5 ° C. in an atmosphere with a He flow rate of 100 cm ³ / min.
The weight loss curve at 5 / min was measured, and the temperature at which the weight loss was 5% was defined as the thermal decomposition start temperature. The measurement results are summarized in Table 1.

[0063]

[Table 1]

Example 2 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3
80 g of 3,3-hexafluoropropane (A) (central glass) and 1-perfluorononenyloxy-3,5
-Phthaloylbis (4- (4-cyanamidephenoxy)
10 g of (C) (manac) and 10 g of 4,4′-diphenylmethane bismaleimide (E) (Mitsui Toatsu) were dissolved in 100 g of methyl isobutyl ketone, and the mixture was heated at 100 ° C. and 60 ° C.
Prepolymerization was carried out under reflux for minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

Example 3 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3
80 g of 3,3-hexafluoropropane (A) (central glass) and 1-perfluorononenyloxy-3,5
-Phthaloylbis (4- (4-cyanamidephenoxy)
10 g of (C) (Manac) and 10 g of 4,4'-dicyanamide diphenyl ether (F) (Manac) were dissolved in 100 g of methyl isobutyl ketone, and the mixture was heated at 100 ° C and 60 ° C.
Prepolymerization was carried out under reflux for minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

Example 4 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3
80 g of 3,3-hexafluoropropane (A) (central glass) and 1-perfluorononenyloxy-3,5
-Phthaloylbis (4- (4-cyanamidephenoxy)
10 g of (C) (manac) and 10 g of 4,4'-diphenylmethane diisocyanate (G) (Takeda Yakuhin) were dissolved in 100 g of methyl isobutyl ketone, and the mixture was heated at 100 ° C and 60 ° C.
Prepolymerization was carried out under reflux for minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

Example 5 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3
80 g of 3,3-hexafluoropropane (A) (central glass) and 1-perfluorononenyloxy-3,5
-Phthaloylbis (4- (4-cyanamidephenoxy)
(C) (Manac) 10 g and bisphenol A type epoxy compound DER323 (H) (Dow Chemical) 10
g to 100 g of methyl isobutyl ketone,
Prepolymerization was performed under reflux at 60 ° C for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample.
The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed.
The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

Example 6 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3
80 g of 3,3-hexafluoropropane (A) (central glass) and 1-perfluorononenyloxy-3,5
-Phthaloylbis (4- (4-cyanamidephenoxy)
(C) (Manac) 10 g and p-divinylbenzene
(I) (Wako Pure Chemical Industries, Ltd.) 10 g of methyl isobutyl ketone 10
It was dissolved in 0 g and subjected to prepolymerization under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing conditions are 150 ° C., and once the sample is melted, 250
The temperature was raised to ° C and pressure was applied. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

Example 7 2,2-bis (4- (4-maleimido-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) ( 80 g of central glass) and 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-
Cyanamide phenoxy) (D) (Manac) 20 g is melt | dissolved in 100 g of methyl isobutyl ketones, 100 degreeC and 6
Prepolymerization was carried out under reflux for 0 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing conditions are 150 ° C for the sample,
Once melted, the temperature was raised to 250 ° C. and pressure was applied. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

Example 8 2,2-bis (4- (4-maleimido-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) ( 80 g of central glass) and 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-
Cyanamide phenoxy) (D) (Manac) 10 g and 4,4'-diphenylmethane bismaleimide (E)
(Mitsui Toatsu) 10 g methyl isobutyl ketone 100 g
And was prepolymerized under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

Example 9 2,2-bis (4- (4-maleimido-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) ( 80 g of central glass) and 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-
Cyanamide phenoxy) (D) (Manac) 10 g and 4,4'-dicyanamide diphenyl ether (F)
(Manac) 10 g methyl isobutyl ketone 100 g
And was prepolymerized under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

<Embodiment 10> 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 g and 1-perfluorononenyloxy-3,5-phthaloylbis ( 4- (4
-Cyanamidephenoxy) (D) (Manac) and 10 g of 4,4'-diphenylmethane diisocyanate (G) (Takeda Yakuhin) were added to methyl isobutyl ketone 1
It was dissolved in 00 g and subjected to prepolymerization under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate.
The curing conditions are 150 ° C. and once the sample is melted,
The temperature was raised to 0 ° C. and pressure was applied. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

<Embodiment 11> 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 g and 1-perfluorononenyloxy-3,5-phthaloylbis ( 4- (4
-Cyanamide phenoxy) (D) (Manac) 10 g and bisphenol A type epoxy compound DER323
10 g of (H) (Dow Chemical) was dissolved in 100 g of methyl isobutyl ketone, and prepolymerized at 100 ° C. under reflux for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing conditions are 150 ° C., after melting the sample once,
The temperature was raised to 250 ° C. and pressure was applied. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

<Embodiment 12> 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 g and 1-perfluorononenyloxy-3,5-phthaloylbis ( 4- (4
-Cyanamidephenoxy) (D) (Manac) 10 g and p-divinylbenzene (I) (Wako Pure Chemical Industries, Ltd.) 10 g were dissolved in methyl isobutyl ketone 100 g,
Prepolymerization was carried out under reflux for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

Comparative Example 1 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) 80 g and 4,4'-
Dicyanamide diphenyl ether (F) (Manac) 2
Dissolve 0 g in 100 g of methyl isobutyl ketone,
Prepolymerization was performed under reflux at 0 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. Curing condition is 150 ℃
The sample was once melted, heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength,
The thermal decomposition temperature was measured.

Comparative Example 2 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) 80 g and 4,4'-
Dicyanamide diphenyl ether (F) (Manac) 10
g and 4,4'-diphenylmethane diisocyanate (G) (Takeda Yakuhin) 10 g with methyl isobutyl ketone 1
It was dissolved in 00 g and subjected to prepolymerization under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate.
The curing conditions are 150 ° C. and once the sample is melted,
The temperature was raised to 0 ° C. and pressure was applied. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

Comparative Example 3 80 g of 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) and 4,4'-
Dicyanamide diphenyl ether (F) (Manac) 1
0g and bisphenol A type epoxy compound DER3
10 g of 23 (H) (Dow Chemical) was dissolved in 100 g of methyl isobutyl ketone, and prepolymerization was performed under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The thickness of the obtained sample is 2
A resin plate of a cured product was obtained by press molding using a spacer of mm. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured. <Comparative Example 4> 80 g of 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) and 10 g of 4,4'-dicyanamide diphenyl ether (F) (Manac) and p
Divinylbenzene (I) (Wako Pure Chemical Industries, Ltd.) (10 g) was dissolved in methyl isobutyl ketone (100 g), and prepolymerization was performed under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.

Compounds (A) used in Examples and Comparative Examples
(I) is as follows, and the properties of the obtained cured product are shown in Table 1.

[0079]

[Chemical formula 24]

<Embodiment 13> 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
80 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
A resin composition comprising 20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (manac) and 0.5 part by weight of a peroxide as a polymerization initiator was dissolved in a solvent dimethylformamide to obtain 50%. The solution was prepared, shaken and stirred and used as a varnish.

A varnish was impregnated and coated on a N glass material T glass cloth (thickness: 60 μm) which was a reinforcing material, and dried in constant temperature air at 150 ° C. for 10 minutes to obtain a prepreg. 10 sheets of the obtained prepreg are piled up, and pressure is 30 kgf / c in the press.
m ^2, was heated for 30 minutes at 130 ° C., further 250 ° C.
After that, the adhesive was cured for 1 hour to obtain a laminated plate. As a sample for measuring the copper foil peel strength, 10 prepregs were stacked, and copper foil (manufactured by Furukawa Electric Co., Ltd., thickness 70 μm) was stacked on both surfaces and laminated and bonded under the same conditions. The characteristics of the sample manufactured by the above method were evaluated. The relative dielectric constant was calculated by measuring the capacitance of the sample according to JIS-C-6481 using an LF impedance analyzer 4192A manufactured by Hewlett-Packard Company. Copper foil peel strength is measured using Fudo Industrial Rheometer NRM-3101D according to JIS-C-64
According to No. 81, the peel strength of the copper foil in the vertical direction was measured under the condition of the peeling speed of 50 mm / min. Regarding the thermal decomposition start temperature, high-speed differential thermal balance TGD-7000R manufactured by Vacuum Riko Co., Ltd.
It was measured using H. About 10 mg of a powder sample obtained by crushing a resin component, a heating weight loss curve was measured at a temperature rising rate of 5 ° C./min in an atmosphere with a He flow rate of 100 cm ³ / min, and the temperature showing 5% weight loss was defined as the pyrolysis start temperature. .. Regarding the coefficient of thermal expansion, vacuum mechanical engineering thermomechanical property measuring device TM-30
No. 00 was used to measure the coefficient of thermal expansion (50-220 ° C.) in the thickness direction of the sample cut out from the laminated plate into 7 mm × 7 mm. The measurement was performed in a compression mode with a temperature rising rate of 2 ° C./min and a load of 10 g.
The flame retardancy was measured by UL-94. The measurement results are summarized in Table 2.

[0082]

[Table 2]

<Embodiment 14> 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
80 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
A varnish was prepared by using a resin composition containing 20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (manac) and 0.5 part by weight of a peroxide as a polymerization initiator. The adjusting method was in accordance with the method shown in Example 13. Using this varnish, the aromatic amide type organic synthetic fiber woven Kevlar 49 made by DuPont as a reinforcing material was used as a reinforcing material for prepreg and lamination. A plate was prepared and its properties were evaluated, and the results are shown in Table 2.

<Embodiment 15> 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
80 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
A varnish was prepared using a resin composition comprising 20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (manac) and 0.5 part by weight of a peroxide as a polymerization initiator. The adjusting method was in accordance with the method shown in Example 13. Using this varnish, a prepreg was prepared in the same manner as in Example 13, using the aromatic amide organic synthetic fiber nonwoven fabric GAU-505-50 manufactured by Nippon Aroma Co. as a reinforcing material. A laminated plate was prepared and the characteristics were evaluated, and the results are shown in Table 2.

Example 16 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Diphenylmethane bismaleimide (E) (Mitsui Toatsu) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, Nitto Boseki T was used as a reinforcing material in the same manner as in Example 13.
Using a glass cloth (thickness: 60 μm), a prepreg and a laminated board were produced and the characteristics were evaluated. The results are shown in Table 2.

Example 17 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Diphenylmethane bismaleimide (E) (Mitsui Toatsu) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminate were prepared by using the aromatic amide organic synthetic fiber woven Kevlar 49 manufactured by DuPont as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated. The results are shown in Table 2.

<Embodiment 18> 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Diphenylmethane bismaleimide (E) (Mitsui Toatsu) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, the aromatic amide organic synthetic fiber nonwoven fabric GAU-505 manufactured by Nippon Aroma Co., Ltd. was used as a reinforcing material in the same manner as in Example 13.
50 was used to prepare a prepreg and a laminated board, and the characteristics were evaluated. The results are shown in Table 2.

Example 19 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Dicyanamide diphenyl ether (F) (Manac) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, Nitto Boseki T was used as a reinforcing material in the same manner as in Example 13.
Using a glass cloth (thickness: 60 μm), a prepreg and a laminated board were produced and the characteristics were evaluated. The results are shown in Table 2.

<Embodiment 20> 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Dicyanamide diphenyl ether (F) (Manac) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminate were prepared by using the aromatic amide organic synthetic fiber woven Kevlar 49 manufactured by DuPont as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated. The results are shown in Table 2.

Example 21 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Dicyanamide diphenyl ether (F) (Manac) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, the aromatic amide organic synthetic fiber nonwoven fabric GAU-505 manufactured by Nippon Aroma Co., Ltd. was used as a reinforcing material in the same manner as in Example 13.
50 was used to prepare a prepreg and a laminated board, and the characteristics were evaluated. The results are shown in Table 2.

<Embodiment 22> 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 parts by weight, 1-perfluorononenyloxy-3,5- Phthaloylbis (4-
(4-Cyanamide phenoxy) (D) (Manac) 20
A varnish was prepared by using a resin composition comprising 1 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminated board were manufactured by using Nitto Boseki T glass cloth (thickness 60 μm) as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated. The results are shown in Table 2.

Example 23 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 parts by weight, 1-perfluorononenyloxy-3,5- Phthaloylbis (4-
(4-Cyanamide phenoxy) (D) (Manac) 20
A varnish was prepared by using a resin composition comprising 1 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminate were prepared by using the aromatic amide organic synthetic fiber woven Kevlar 49 manufactured by DuPont as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated. The results are shown in Table 2.

Example 24 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 parts by weight, 1-perfluorononenyloxy-3,5- Phthaloylbis (4-
(4-Cyanamide phenoxy) (D) (Manac) 20
A varnish was prepared by using a resin composition comprising 1 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, the aromatic amide organic synthetic fiber non-woven fabric GAU-505-5 manufactured by Nippon Aroma Co., Ltd. was used as a reinforcing material in the same manner as in Example 13.
0 was used to prepare a prepreg and a laminated plate, and the characteristics were evaluated. The results are shown in Table 2.

Comparative Example 5 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) 80 parts by weight and 4,
A varnish was prepared using a resin composition containing 20 parts by weight of 4'-dicyanamide diphenyl ether (F) (Manac) and 0.5 parts by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminated board were manufactured by using Nitto Boseki T glass cloth (thickness 60 μm) as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated. The results are shown in Table 2.

Comparative Example 6 80 parts by weight of 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) and 4,
A varnish was prepared using a resin composition containing 20 parts by weight of 4'-dicyanamide diphenyl ether (F) (Manac) and 0.5 parts by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminate were prepared by using the aromatic amide organic synthetic fiber woven Kevlar 49 manufactured by DuPont as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated.
The results are shown in Table 2.

<Comparative Example 7>4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) 80 parts by weight and 4,
A varnish was prepared using a resin composition containing 20 parts by weight of 4'-dicyanamide diphenyl ether (F) (Manac) and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a aromatic amide organic synthetic fiber nonwoven fabric GAU-5 manufactured by Nippon Aroma Co., Ltd. was used as a reinforcing material in the same manner as in Example 13.
The prepreg and the laminated board were produced using 05-50, and the characteristic was evaluated. The results are shown in Table 2.

<Comparative Example 8> As a comparative example, a polytetrafluoroethylene-based copper clad laminate R47 manufactured by Matsushita Electric Works, Ltd.
37 was evaluated in the same manner as in Example 13.

<Comparative Example 9> As a comparative example, a glass polyimide copper-clad laminate MCL-I-67 manufactured by Hitachi Chemical Co., Ltd.
Was evaluated in the same manner as in Example 13.

Comparative Example 10 As a comparative example, a glass epoxy copper-clad laminate MCL-E-67 manufactured by Hitachi Chemical Co., Ltd.
Was evaluated in the same manner as in Example 13.

The following is an example in which a wiring board was prepared using the laminated materials shown in Examples 13 to 24.

Example 25 Using the prepreg obtained in Example 13, copper foil (70 μm) is heated on both sides in a press at a pressure of 30 kgf / cm ² and a temperature of 130 ° C. for 30 minutes, and further at 250 ° C. The adhesive was cured for 1 hour to obtain a copper-clad laminate. Form circuits on both sides of this copper-clad laminate,
A pin grid array substrate on which an LSI is mounted was created by laminating and adhering via a prepreg. This substrate has a six-layer structure, and each has two surface layers, a power supply layer and a signal layer. The layer structure of this example is shown in FIG.

<Example 26> Using the prepreg obtained in Example 13, a microchip carrier substrate on which an LSI was mounted was prepared in the same manner as in Example 25. This substrate has a six-layer structure, and each has two surface layers, a power supply layer and a signal layer.

Example 27 Example 2 was carried out in the same manner as in Example 25 using the prepreg obtained in Example 13.
A module substrate on which the microchip carrier substrate obtained in No. 6 is mounted was created. This substrate has two surface layers,
It has a 36-layer structure including 10 power supply layers, 16 signal layers, and 8 expansion layers. Also, 81 microchip carrier substrates (9 × 9) can be mounted on this substrate.

Example 28 Example 2 was carried out in the same manner as in Example 25 using the prepreg obtained in Example 13.
A large area substrate on which the module substrate obtained in No. 7 is mounted was created. This substrate has two surface layers and a power supply layer 20.
It has a 54-layer structure consisting of 24 layers of signal layers, and 8 layers of expansion layers. This board also has 64 module boards (8x
8) Can be installed.

Example 29 Example 2 is carried out in the same manner as in Example 25 using the prepreg obtained in Example 15.
A large area substrate on which the module substrate obtained in No. 7 is mounted was created. This substrate has two surface layers and a power supply layer 16
It has a 46-layer structure including a layer, 20 signal layers, and 8 expansion layers. This board also has 36 module boards (6x
6) Can be installed.

As shown in the above embodiment, the present invention enables low dielectric constant and high density mounting.

[0107]

EFFECT OF THE INVENTION The fluorine-containing resin of the present invention is a compound containing fluorine-containing cyanamide in which an imide compound which is excellent as a heat-resistant material has a polar moiety for improving adhesiveness and a fluorine group for lowering the dielectric constant. Used. It was possible to increase the molar specific volume of the cured product obtained by incorporating a large amount of fluorine groups into the structure, and to lower the dielectric constant. Further, since the fluorine group has a large bond dissociation energy with carbon, it was possible to improve the thermal decomposition temperature, which is a measure of heat resistance, and mechanical strength at the same time. Further, since the cyanamide group is fast-curing, workability is excellent. As described above, it was confirmed that the thermosetting resin composed of the fluorinated cyanamide and the fluorinated imide had excellent moldability, and the obtained cured product had excellent heat resistance and mechanical properties. Further, the relative permittivity, which is important for the electrical characteristics of the insulating material, can be reduced, and it can be a material suitable for fields requiring a low permittivity such as a mold material, a wiring board, and an interlayer insulating film of an LSI. Can be expected. In the computer configured with this multilayer board, the dielectric constant of the insulating layer and the density of the insulating layer can be increased, and the operation execution speed is improved.

[Brief description of drawings]

FIG. 1 is a perspective view of a multilayer printed board according to an embodiment of the present invention.

[Explanation of symbols]

1 ... Substrate, 2 ... Circuit, 3 ... Prepreg sheet, 4 ... Through hole.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number FI technical display location C08L 79/08 LRE 9285-4J H01B 3/30 C 9059-5G H01L 23/12 // C08L 25: 18 9166-4J (72) Inventor Satoru Amaba 4026 Kuji Town, Hitachi City, Hitachi, Ibaraki Prefecture Hitachi Research Laboratory, Inc. (72) Yoshinori Kawai 4026 Kuji Town, Hitachi City, Ibaraki Institute Hitachi Research Laboratory, Hitachi Ltd. (72) Inventor Akio Takahashi 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi, Ltd.

Claims (27)

[Claims] 1. A general formula (1): (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ) And a bismaleimide compound represented by the general formula (2): (In the formula, the C ₉ F ₁₇ group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.) A thermosetting resin composition comprising: 2. A thermosetting resin composition, wherein the bismaleimide compound of claim 1 and the biscyanamide compound are used in a mixing ratio of 95: 5 to 5:95. 3. General formula (1): (In the formula, R represents hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ) And a bismaleimide compound represented by the general formula (2): (In the formula, the C ₉ F ₁₇ group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.), And a biscyanamide compound, Maleimide compound, cyanamide compound, cyanato compound, isocyanato compound, epoxy compound,
A thermosetting resin composition comprising at least one kind of a vinyl compound. 4. The resin composition according to claim 1, 2 or 3, wherein the resin composition is dissolved in a solvent to prepare a uniform varnish. 5. A compound represented by the general formula (1): (In the formula, R represents hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ) And a bismaleimide compound represented by the general formula (2): (In the formula, the C ₉ F ₁₇ group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.) A method for producing a cured resin product, characterized in that a three-dimensional crosslinked cured product is obtained by a polymerization reaction of multiple bonds. 6. The method for producing a resin cured product according to claim 5, wherein the polymerization reaction of multiple bonds is heat polymerization. 7. The method for producing a cured resin product according to claim 5, wherein the polymerization reaction of the multiple bonds is polymerization in the presence of an anionic polymerization initiator such as an alkoxy compound. 8. The method for producing a cured resin product according to claim 5, wherein the polymerization reaction of the multiple bonds is polymerization in the presence of a radical polymerization initiator such as peroxide. 9. The method for producing a cured resin product according to claim 5, wherein the polymerization reaction of multiple bonds is photopolymerization such as UV irradiation. 10. A compound represented by the general formula (1): (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ) And a bismaleimide compound represented by the general formula (2): (In the formula, the C ₉ F ₁₇ group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.) A cured product obtained by three-dimensionally crosslinking a resin composition by a polymerization reaction of multiple bonds. 11. The cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is heat polymerization. 12. The cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is polymerization in the presence of an anionic polymerization initiator such as an alkoxy compound. 13. The resin cured product according to claim 10, wherein the polymerization reaction of multiple bonds is polymerization in the presence of a radical polymerization initiator such as a peroxide. 14. The cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is photopolymerization such as UV irradiation. 15. The cured product according to claim 10, which has a relative dielectric constant of 3 or less. 16. A compound represented by the general formula (1): (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ) And a bismaleimide compound represented by the general formula (2): (In the formula, the C ₉ F ₁₇ group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.) An electrical insulator using a cured product obtained by three-dimensionally crosslinking a resin composition containing the same by a polymerization reaction of multiple bonds. 17. A prepreg obtained by impregnating an inorganic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4. 18. A prepreg obtained by impregnating an organic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4. 19. A laminate material using the resin composition according to claim 1, 2, 3 or 4. 20. A laminated material using the resin composition according to claim 1, 2, 3 or 4 together with other resin components. 21. A laminated material obtained by laminating and adhering a prepreg obtained by impregnating an inorganic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4. 22. A laminated material obtained by laminating and adhering a prepreg obtained by impregnating an organic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4. 23. A wiring board comprising the resin composition according to any one of claims 1 to 22 and a laminated material using the composition. 24. A large-area substrate composed of the resin composition according to claim 1 and a laminated material using the composition. 25. A module substrate composed of the resin composition according to claim 1 and a laminated material using the composition. 26. A microchip carrier substrate composed of the resin composition according to any one of claims 1 to 22 and a laminated material using the composition. 27. A pin grid array substrate composed of the resin composition according to any one of claims 1 to 22 and a laminated material using the composition.