JPH05140304A - Fluorine-containing bismaleimide resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having good heat resistance and adhesion and low specific dielectric constant and free from producing a by product by blending a specific bismaleimide compound with a biscyanamide compound. CONSTITUTION:(A) A bismaleimide compound expressed by formula I (C9F17 group is perfluorononenyl group having one double bond; X is divalent group containing an ester bond or ether bond) is blended with (B) a biscyanamide compound expressed by formula II [R is H, alkyl or halogen; (n) is 1-4]. The components A and B are blended at a ratio of (95:5) to (5:95).

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 large relative permittivity 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 It is generally known that a polar functional group such as ester may be introduced in order to improve the adhesiveness, but the relative dielectric constant is increased by the usual method.

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]

(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.). Compound and general formula (2)

[0009]

[Chemical 12]

A thermosetting resin composition comprising a biscyanamide compound represented by the formula (wherein R is hydrogen, an alkyl group, or halogen, and n is an integer of 1 to 4). [Claim 2] The mixing ratio of the bismaleimide compound of Claim 1 and the biscyanamide compound of Claim 1 is 95: 5
A thermosetting resin composition, which is used at 5:95. Claim 3 General formula (1)

[0011]

[Chemical 13]

(In the formula, the C ₉ F ₁₇ group represents a perfluorononenyl group having one double bond, and X represents a divalent group containing an ester bond or an ether bond.). Compound and general formula (2)

[0013]

[Chemical 14]

(In the formula, R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4.), a maleimide compound, a cyanamide compound, a cyanato compound, an isocyanato compound, and an epoxy. A thermosetting resin composition comprising at least one of a 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)

[0017]

[Chemical 15]

(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.) Maleimide compound and general formula (2)

[0019]

[Chemical 16]

(In the formula, R is hydrogen, an alkyl group, or halogen, and n is an integer of 1 to 4.) A three-dimensional crosslinked cured product is obtained by a polymerization reaction of multiple bonds using a biscyanamide compound. A method for producing a cured resin product, which comprises:

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 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)

[0026]

[Chemical 17]

(In the formula, the C ₉ F ₁₇ group represents a perfluorononenyl group having one double bond, and X represents a divalent group containing an ester bond or an ether bond.). Compound and general formula (2)

[0028]

[Chemical 18]

(Wherein R is hydrogen, an alkyl group, or halogen, and n is an integer of 1 to 4), a resin composition containing a biscyanamide compound is three-dimensionally polymerized by a multiple bond polymerization reaction. A cured product obtained by crosslinking.

11. A cured resin product according to claim 10, wherein the polymerization reaction of 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)

[0036]

[Chemical 19]

(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). Maleimide compound and general formula (2)

[0038]

[Chemical 20]

(In the formula, R is hydrogen, an alkyl group, or halogen, and n is an integer of 1 to 4.) A resin composition containing a biscyanamide compound is three-dimensionally polymerized by a multiple bond polymerization reaction. An electrical insulator using a cured product obtained by crosslinking.

(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 laminate 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 claims 1 to 22 and a laminated material using the resin 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 resin composition.

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

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

27. A pin grid array substrate comprising the resin composition according to any one of claims 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.

[0052]

[Chemical 21]

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

[0054]

[Chemical formula 22]

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

[0056]

[Chemical formula 23]

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

By using these compounds as a composition of thermosetting resin, the moldability of the resin can be improved, and at the same time, since it has a fluorine-substituted substituent, it is excellent in heat resistance and has a relative dielectric constant. It was possible to obtain a resin having a low

A thermosetting resin using a fluorinated cyanamide compound and a fluorinated maleimide compound has a heat resistance due to the formation of a melamine ring which is a heteroaromatic ring or an melamine ring and an imide ring which are heteromelamine rings by a trimerization reaction such as heating, and complicated three-dimensional crosslinking. 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 no reaction by-product such as condensed water is 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 mold molding. This is different from typical heat-resistant insulating materials such as polyimide, polybenzimidazole, and polybenzothiazole.

[0060]

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.

[0061]

EXAMPLES The present invention will be described in detail with reference to examples below, but the present invention is not limited to these examples.

Example 1 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (A) (neos) and 2,2-bis (4- (4-cyanamide) Phenoxy) phenyl) -1,
1,1,3,3,3-hexafluoropropane (C)
20 g of (Manac) 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 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 characteristics of the obtained resin plate were evaluated.
The relative permittivity was measured by using LF impedance analyzer 4192A manufactured by Hewlett-Packard Co., JIS-C-
According to 6481, the capacitance of the sample was measured and the relative permittivity was calculated. Regarding the coefficient of thermal expansion, 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 was measured using a thermomechanical property measuring device TM-3000 manufactured by Vacuum Riko. 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 is Shimadzu's Autograph DDS
It was measured according to JIS-C-6481 using -5000. 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. For a powder sample 10 mg 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. did. The flame retardancy was measured by UL-94. The measurement results are shown in Table 1.

[0063]

[Table 1]

Example 2 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (A) (neos) and 2,2-bis (4- (4-cyanamide) Phenoxy) phenyl) -1,
1,1,3,3,3-hexafluoropropane (C)
(Manac) and 10 g of 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) were 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 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 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (A) (neos) and 2,2-bis (4- (4-cyanamide) Phenoxy) phenyl) -1,
1,1,3,3,3-hexafluoropropane (C)
10 g of (Manac) and 10 g of 4,4'-dicyanamide diphenyl ether (F) (Manac) were dissolved in 100 g of methyl isobutyl ketone, and 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 4 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (A) (neos) and 2,2-bis (4- (4-cyanamide) Phenoxy) phenyl) -1,
1,1,3,3,3-hexafluoropropane (C)
10 g of (MANAC) and 10 g of 4,4'-diphenylmethane diisocyanate (G) (Takeda Pharmaceutical Co., Ltd.) were dissolved in 100 g of methyl isobutyl ketone, and prepolymerization was carried out 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 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 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (A) (neos) and 2,2-bis (4- (4-cyanamide) Phenoxy) phenyl) -1,
1,1,3,3,3-hexafluoropropane (C)
10 g of (Manac) and 10 g of bisphenol A type epoxy compound DER323 (H) (Dow Chemical) were 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 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 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (A) (neos) and 2,2-bis (4- (4-cyanamide) Phenoxy) phenyl) -1,
1,1,3,3,3-hexafluoropropane (C)
(Manac) 10 g and p-divinylbenzene (I)
(Wako Pure Chemical Industries, Ltd.) 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 7 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (B) (neos) and 2,2-bis (4- (4-cyanamide) 20 g of 2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (D) (Manac) was dissolved in 100 g of methyl isobutyl ketone, and the prepolymer was refluxed at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample, which was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The condition is 150 ℃, sample once,
After melting, 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 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (B) (neos) and 2,2-bis (4- (4-cyanamide) -2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (D) (Manac) 10 g and 4,
4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu)
Dissolve 10 g in 100 g of methyl isobutyl ketone,
Prepolymerization was carried out under reflux at 00 ° 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.

Example 9 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (B) (neos) and 2,2-bis (4- (4-cyanamide) -2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (D) (Manac) 10 g and 4,
10 g of 4'-dicyanamide diphenyl ether (F) (Manac) 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 obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition is 15
The sample was once melted at 0 ° C., 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 10 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (B) (neos) and 2,2-bis (4- (4-cyanamide) -2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (D) (Manac) 10 g and 4,
10 g of 4'-diphenylmethane diisocyanate (G) (Takeda Yakuhin) was dissolved in 100 g of methyl isobutyl ketone, and prepolymerization was carried out 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. Curing condition is 1
The sample was once melted at 50 ° C., 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 11 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (B) (neos) and 2,2-bis (4- (4-cyanamide) 2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (D) (Manac) 10 g and bisphenol A type epoxy compound DER323 (H) (Dow Chemical) 10 g Methyl isobutyl ketone 100g
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 12 80 g of 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) (B) (neos) and 2,2-bis (4- (4-cyanamide) -2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (D) (Manac) 10 g and p-
10 g of divinylbenzene (I) (Wako Pure Chemical Industries, Ltd.) 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 obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition is 150 ° C.
After melting, 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.

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]

Example 13 1-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (A) (Neos) 80 parts by weight, 2,2-bis (4-) (4-cyanamide phenoxy)
A resin composition comprising 20 parts by weight of phenyl) -1,1,1,3,3,3-hexafluoropropane (C) (Manac) and 0.5 part by weight of a peroxide as a polymerization initiator was added to a solvent dimethylformamide. The solution was dissolved and a 50% 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 a temperature 220 ° 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 permittivity is determined by Hewlett Packard LF Impedance Analyzer 4192A.
Was used to measure the capacitance of the sample according to JIS-C-6481, and the relative permittivity was calculated. Copper foil peel strength is measured by using Fudo Kogyo rheometer NRM-3101D, JIS-C-
According to 6481, the copper foil peel strength in the vertical direction was measured under the condition of a peeling speed of 50 mm / min. Regarding the thermal decomposition start temperature, high-speed differential thermal balance TGD-700 manufactured by Vacuum Riko Co., Ltd.
It was measured using 0RH. For a powder sample 10 mg 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. did. Regarding the coefficient of thermal expansion, vacuum mechanical engineering thermomechanical property measuring device TM-
Using 3000, the thermal expansion coefficient (50-220 ° C.) in the thickness direction of the sample cut out from the laminated plate into 7 mm × 7 mm 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. The flame retardancy was measured by UL-94. The measurement results are summarized in Table 2.

[0082]

[Table 2]

Example 14 1-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (A) (Neos) 80 parts by weight, 2,2-bis (4-) (4-cyanamide phenoxy)
A varnish was prepared by using a resin composition comprising 20 parts by weight of phenyl) -1,1,1,3,3,3-hexafluoropropane (C) (Manac) and 0.5 parts by weight of a peroxide as a polymerization initiator. It was adjusted. 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 15 1-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (A) (Neos) 80 parts by weight, 2,2-bis (4-) (4-cyanamide phenoxy)
A varnish was prepared by using a resin composition comprising 20 parts by weight of phenyl) -1,1,1,3,3,3-hexafluoropropane (C) (Manac) and 0.5 parts by weight of a peroxide as a polymerization initiator. It was adjusted. 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 nonwoven fabric GAU-505-50 manufactured by Japan Aroma Co., Ltd. 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 16 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (A) (neos) 70 parts by weight, 2,2-bis (4-) (4-cyanamide phenoxy)
Phenyl) -1,1,1,3,3,3-hexafluoropropane (C) (Manac) 20 parts by weight, and 4,4 '
-Diphenylmethane bismaleimide (E) (Mitsui Toatsu)
A varnish was prepared using a resin composition consisting of 10 parts by weight 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. This varnish was used in the same manner as in Example 13 to prepare a prepreg by using Nitto Boseki T glass cloth (thickness 60 μm) as a reinforcing material.
A laminated board was prepared and its characteristics were evaluated. The results are shown in Table 2.

Example 17 1-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (A) (Neos) 70 parts by weight, 2,2-bis (4-) (4-cyanamide phenoxy)
Phenyl) -1,1,1,3,3,3-hexafluoropropane (C) (Manac) 20 parts by weight, and 4,4 '
-Diphenylmethane bismaleimide (E) (Mitsui Toatsu)
A varnish was prepared using a resin composition consisting of 10 parts by weight 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.

Example 18 1-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (A) (Neos) 70 parts by weight, 2,2-bis (4-) (4-cyanamide phenoxy)
Phenyl) -1,1,1,3,3,3-hexafluoropropane (C) (Manac) 20 parts by weight, and 4,4 '
-Diphenylmethane bismaleimide (E) (Mitsui Toatsu)
A varnish was prepared using a resin composition consisting of 10 parts by weight 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, 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.
Using -50, a prepreg and a laminated board were produced and the characteristics were evaluated. The results are shown in Table 2.

Example 19 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (A) (neos) 70 parts by weight, 2,2-bis (4-) (4-cyanamide phenoxy)
Phenyl) -1,1,1,3,3,3-hexafluoropropane (C) (Manac) 20 parts by weight, and 4,4 '
A varnish was prepared using a resin composition containing 10 parts by weight of 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 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 20 1-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (A) (Neos) 70 parts by weight, 2,2-bis (4-) (4-cyanamide phenoxy)
Phenyl) -1,1,1,3,3,3-hexafluoropropane (C) (Manac) 20 parts by weight, and 4,4 '
-Dicyanamide diphenyl ether (F) (Manac)
A varnish was prepared using a resin composition consisting of 10 parts by weight 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.

Example 21 1-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (A) (Neos) 70 parts by weight, 2,2-bis (4-) (4-cyanamide phenoxy)
Phenyl) -1,1,1,3,3,3-hexafluoropropane (C) (Manac) 20 parts by weight, and 4,4 '
-Dicyanamide diphenyl ether (F) (Manac)
A varnish was prepared using a resin composition consisting of 10 parts by weight 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, 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.
Using -50, a prepreg and a laminated board were produced and the characteristics were evaluated. The results are shown in Table 2.

Example 22 1-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (B) (Neos) 80 parts by weight, 2,2-bis (4-) (4-Cyanamide-2-trifluoromethylphenoxy) phenyl) -1,1,1,
A varnish was prepared using a resin composition comprising 20 parts by weight of 3,3,3-hexafluoropropane (D) (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 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 1-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (B) (Neos) 80 parts by weight, 2,2-bis (4-) (4-Cyanamide-2-trifluoromethylphenoxy) phenyl) -1,1,1,
A varnish was prepared using a resin composition comprising 20 parts by weight of 3,3,3-hexafluoropropane (D) (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 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 1-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-maleimidophenoxy) phenyl) (B) (Neos) 80 parts by weight, 2,2-bis (4-) (4-Cyanamide-2-trifluoromethylphenoxy) phenyl) -1,1,1,
A varnish was prepared using a resin composition comprising 20 parts by weight of 3,3,3-hexafluoropropane (D) (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 5 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) 80 parts by weight, 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), 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> 80 parts by weight of 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu), 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 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 results of the above Examples and Comparative Examples are summarized in Table 2.

An example in which a wiring board is prepared by using the laminated materials shown in Examples 13 to 24 will be shown below.

Example 25 Using the prepreg obtained in Example 13, copper foil (70 μm) on both sides was heated in a press at a pressure of 30 kgf / cm ² and a temperature of 130 ° C. for 30 minutes, and further at 200 ° 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, each having two surface layers, a power supply layer and a signal layer.

<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 Using the prepreg obtained in Example 13 and in the same manner as in Example 25, Example 2
A module substrate on which the microchip carrier substrate obtained in No. 6 was mounted was prepared. 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 Using the prepreg obtained in Example 13 and in the same manner as in Example 25, Example 2
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. In addition, 36 (6 × 6) of the above module substrates can be mounted on this substrate.

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

[0108]

EFFECT OF THE INVENTION The fluorine-containing resin of the present invention is a fluorinated cyanamide compound having a polar moiety for improving the adhesiveness and a fluorine group for lowering the dielectric constant of an imide compound which is excellent as a heat-resistant material. 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 simultaneously improve the thermal decomposition temperature, which is a measure of heat resistance, and the mechanical strength. 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 has excellent moldability, and the obtained cured product has excellent heat resistance and mechanical properties. Furthermore, the relative permittivity, which is important for the electrical characteristics of the insulating material, can be reduced, and it can be expected to be a material suitable for fields requiring low permittivity such as molding materials, wiring boards, and interlayer insulating films of LSIs. .. 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 code Internal reference number FI technical display location C08L 79/08 LRE 9285-4J H01B 3/30 9059-5G H01L 23/12 // C08L 35:00 7921-4J (72) Inventor Masahiro Suzuki 4026, Kujimachi, Hitachi City, Hitachi, Ibaraki Prefecture, Hitachi Research Laboratory, Inc. 72) Inventor Akio Takahashi 4026 Kuji Town, Hitachi City, Ibaraki Prefecture, Hitachi Research Laboratory, Hiritsu Manufacturing Co., Ltd.

Claims (27)

[Claims] 1. A general formula (1): (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). , The general formula (2): (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. The thermosetting resin composition characterized by including the biscyanamide compound represented by these. 2. A mixing ratio of the bismaleimide compound of claim 1 and the biscyanamide compound of claim 1 of 95: 5 to 5:95.
And a thermosetting resin composition. 3. General formula (1): (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). , The general formula (2): (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ), And a thermosetting resin composition comprising 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 and forming a uniform varnish. 5. A compound represented by the general formula (1): (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). , The general formula (2): (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. 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 using the biscyanamide compound represented by the formula (1). 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, 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 bismaleimide compound represented by the following formula: General formula (2) (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. A cured product obtained by three-dimensionally cross-linking a resin composition containing a biscyanamide compound represented by) 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, 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 bismaleimide compound represented by the following formula: General formula (2) (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. An electric insulator using a cured product obtained by three-dimensionally cross-linking a resin composition containing a biscyanamide compound represented by the formula (3) 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 composed of the resin composition according to claim 1 and a laminated material using the resin composition. 24. A large area substrate composed of the resin composition according to claim 1 and a laminated material using the resin 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.