JP3348490B2 - Cyanate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cyanate resin composition. INDUSTRIAL APPLICABILITY The cyanate resin composition of the present invention is particularly useful as a resin for a laminate in electric / electronic applications requiring low dielectric properties, and is also applicable to sealing applications and molding resins.

[0002]

2. Description of the Related Art Conventionally, among thermosetting resin compositions used for electric and electronic applications, as a material for a printed wiring board, a combination of a bisphenol type epoxy resin and dicyandiamide, or a bismaleimide compound and an amine compound is mainly used. Is used. In recent years, with the increase in the number of layers in printed wiring boards, low dielectric properties of resins have been demanded mainly for the purpose of improving signal speed, and conventional thermosetting resin compositions have been used as a means for responding to this demand. Although addition of a dielectric thermoplastic resin is well known, according to this method, a drawback that impairs the heat resistance and the like of the thermosetting resin is pointed out, and the requirement of a low dielectric resin that can withstand practical use is sufficiently satisfied. Could not.

[0003] From these points, cyanate resins have been developed and are disclosed in German Patent No. 2,533,122 and International Patent No. 88/054.
No. 43, etc. As a cyanate resin generally used at present, dicyanate of bisphenol A is known, but with the advancement of computer technology, further lowering of dielectric constant has been required. Also,
It is known that the above-mentioned cyanate compound is generally used as a resin composition, and is commonly used with a bismaleimide or an epoxy compound (Japanese Patent Publication No. 54-30440) according to the required properties. However, in this case, the dielectric constant of the resin composition increased significantly, and did not reach a satisfactory level.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cyanate resin composition which is excellent in low dielectric properties and provides a cured product having heat resistance enough for practical use.

[0005]

The present inventors have made intensive studies on the skeleton structure of the cyanate compound and found that t
-Increase in molecular volume due to bulkiness of butyl group and increase in non-polarity due to large hydrophobic group greatly contribute to low dielectric constant,
It has been found that a composition of a specific cyanate having this satisfies the above object, and has accomplished the present invention.
That is, the present invention is as follows. (1) The following general formula (1)

[0006]

Embedded image (Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A is an alkyl group having 1 to 3 carbon atoms, and i is 0 to 3 A cyanate compound represented by the following integer value) or a prepolymer thereof and a curing agent as essential components:

(2) A cyanate resin composition comprising a cyanate compound represented by the general formula (1) or a prepolymer thereof, a brominated epoxy compound or a prepolymer thereof, and a curing agent as essential components. .

(3) A cyanate compound represented by the general formula (1) or a prepolymer thereof, a curing agent, and a polymaleimide compound having two or more N-maleimide groups in a molecule or a prepolymer thereof are essential. A cyanate resin composition characterized by comprising as a component. The cyanate compound which is an essential component of the resin composition of the present invention has the following general formula (1)
0)

[0009]

Embedded image (Wherein R ₁ , R ₂ , A and i are defined in the same manner as in the general formula (1)) and a halogenated cyanide represented by chlorocyan and bromocyan. It can be obtained by performing a dehydrohalogenation reaction in the presence of a base in an organic solvent.

The above-mentioned bisphenols can be used by any known method, and a general production method is to react a carbonyl compound with a phenol in the presence of an acid catalyst. However, this is not the case.

As the carbonyl compound, a compound having a carbonyl group having 1 to 11 carbon atoms is used. Examples thereof include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, octylaldehyde and the like. Representative aldehyde compounds, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, ethyl propyl ketone, diethyl ketone, dipropyl ketone, ketone compounds typified by dibutyl ketone, etc., to achieve the object of the present invention Are preferably formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde. Here, as the phenols, those having a t-butyl group at the ortho-position of the OH group, no substituent at the para-position, and optionally having an alkyl group having 3 or less carbon atoms are used. For example, 2-t-butylphenol, 2-t-butyl-5-
Methylphenol, 2-t-butyl-3-methylphenol, 2-t-butyl-6-methylphenol, 2-t
-Butyl-5-ethylphenol, 2-t-butyl-3
-Ethylphenol, 2-t-butyl-3-propylphenol, and the like. In order to achieve the object of the present invention, 2-t-butylphenol, 2-t-butyl-5
-Methylphenol is preferred.

As a typical example of the cyanate compound used in the present invention, the following structural formula (9)

Embedded image The compound represented by these is mentioned.

The polymaleimide compound used in the present invention is a polymaleimide compound containing two or more N-maleimide groups in a molecule, and any compound obtained by any method can be used. Examples of the method of synthesizing the polymaleimide compound include, for example, a method of reacting a starting phenol with p-chloronitrobenzene, and then reacting an amine compound obtained by reduction with maleic anhydride.
It is not limited to this. Examples of preferred polymaleimide compounds for achieving the object of the present invention are as follows. That is, the following general formula (2)

[0014]

Embedded image [Wherein X is the following structural formula (3), (4), (5),
(6), (7) or (8)

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image (In the formula, n-Pr represents an n-propyl group.)

[0019]

Embedded image

[0020]

Embedded image Is a group represented by ).

Examples of the brominated epoxy compound used in the present invention include glycidyl ether of tetrabromobisphenol A and glycidyl ether of brominated phenol novolak. Flame retardancy can be imparted by adding these compounds to the resin composition of the present invention.

The cyanate compound, brominated epoxy compound and polymaleimide compound used in the present invention may be used as a monomer, or may be used alone or as a prepolymer of a mixture thereof. The prepolymer is a mixture of a cyanate compound, a brominated epoxy compound and a polymaleimide compound alone or in combination with a curing agent described below.
It can be obtained by heating to about 200 ° C.

When the brominated epoxy compound or its prepolymer is added to the cyanate compound or its prepolymer to impart flame retardancy, the amount of the brominated epoxy compound or its prepolymer is determined by the amount of the bromo content in the composition. An amount such that it becomes 5 to 50% by weight is preferable. The polymaleimide compound or its prepolymer is preferably 1 to 50% by weight, more preferably 3 to 50% by weight, based on the total amount of these and the cyanate compound or its prepolymer.
It can be mixed at a rate of 35% by weight.

As the curing agent for the resin composition of the present invention, a known curing agent can be used. For example, hydrochloric acid, protonic acid represented by phosphoric acid; aluminum chloride,
Lewis acids represented by boron trifluoride complex and zinc chloride;
Aromatic hydroxy compounds represented by phenol, pyrocatechol, dihydroxynaphthalene; organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate; tertiary such as triethylamine, tributylamine, quinoline, isoquinoline Amines; quaternary ammonium salts represented by tetraethylammonium chloride and tetrabutylammonium bromide; imidazoles; sodium hydroxide, sodium methylate, diazabicyclo- (2,2,2) -octane, triphenylphosphine, or these And the like, but more preferably for achieving the purpose,
Organic metal salts such as zinc naphthenate, cobalt octylate and tin octylate, or a mixture of these organic metal salts and imidazoles are used.

Other thermosetting resins can be used in combination with the resin composition of the present invention as long as the purpose is not impaired. For example, epoxy resins represented by diglycidyl ethers of bisphenol A and bisphenol F, glycidyl ethers of phenol novolak and cresol novolak, bisvinyl benzyl etherified products of bisphenol A and tetrabromobisphenol A, vinyl benzyl ether of diaminodiphenylmethane Alkenyl aryl ether resin represented by
Bisphenol A and tetrabromobisphenol A
Alkynyl ether resins such as dipropargyl ether of diaminodiphenylmethane, propargyl ether of diaminodiphenylmethane, etc., phenol resins, resole resins, allyl ether compounds, allylamine compounds, triallyl cyanurate, triallyl isocyanurate, vinyl group-containing polyolefin Examples include, but are not limited to, compounds. Thermoplastic resins can also be added, including but not limited to polyphenylene ether, polystyrene, polyethylene, polybutadiene, polyimide, and modified products thereof. These resins may be mixed in the cyanate resin composition, or may be used after being reacted in advance.

In the present invention, known additives such as a curing accelerator, a flame retardant, a release agent, a surface treatment agent, and a filler may be added to the composition depending on the use. As a curing accelerator, imidazoles, tertiary amines, phosphorus compounds, alkylphenols, as a flame retardant, antimony trioxide, red phosphorus, etc., as a release agent, waxes, zinc stearate, etc. Examples of the surface treatment agent include a silane coupling agent. Examples of the filler include silica, alumina, talc, clay, and glass fiber.

The cyanate resin composition of the present invention is used for applications such as lamination of printed wiring boards and the like, sealing of electronic parts, and other molding. As a method of making a laminate using the resin composition of the present invention, the resin composition is prepared by methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol dimethyl ether, toluene, xylene, 1,4-dioxane, tetrahydrofuran, Dissolve uniformly using an organic solvent such as dimethylformamide, glass fiber, polyester fiber,
Polyamide fibers, organic fibers such as alumina fibers, woven fabrics made of inorganic fibers, mats, impregnated in a substrate made of paper or a combination thereof, and a method of hot press-molding a prepreg obtained by heating and drying. The method is not limited to the above method.

[0028]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples.

Synthesis Example 1 This synthesis example relates to a method for producing a dicyanate of 1,1-bis (5-tert-butyl-2-methyl-4-hydroxyphenyl) butane, which is a cyanate compound.
200 g (1.05 moleq) of 1,1-bis (5-t-butyl-2-methyl-4-hydroxyphenyl) butane (Sumitomo Chemical Industry Co., Ltd., trade name) was dissolved in 800 g of acetone. Cool to -5 ° C. Chlorsian
After adding 77.3 g (1.26 mol), triethylamine 111.3
g (1.10 mol) is added dropwise over 1 hour, taking care that the reaction temperature does not rise above 0 ° C. After completion of the dropwise addition, the mixture is kept at 2 to 5 ° C. for 1 hour, and then diluted with 500 g of chloroform. After removing salts by filtration, the mixture was washed with water, and the solvent was distilled off under reduced pressure to obtain 194.8 g of a yellow resin.

The cyanate compound obtained in this way, the results of infrared absorption spectrometry, the absorption 3200-3600Cm ^-1 phenolic OH disappeared and it was confirmed to have an absorption 2270 cm ^-1 of the nitrile of cyanate Was.

Synthesis Example 2 This synthesis example relates to a method for producing N, N′-bis (4-aminophenoxyphenyl) menthane bismaleimide, which is a polymaleimide compound used in the present invention. Maleic anhydride 23 in a 5 liter four-necked flask
7.3 g and 2373 g of chlorobenzene were charged and dissolved by stirring under a nitrogen stream. YP-90 (trade name, manufactured by Yashara Chemical, a reaction compound of dipentene and phenol,
After reacting p-chlorobenzene with a hydroxyl equivalent of 162 g / eq), dimethylacetamide (DMA) of (4-aminophenoxyphenyl) menthane obtained by reduction is obtained.
c) Solution (adjusted to a concentration of 34.3% by weight) 1625.
1 g was dropped into the flask at 25 ± 5 ° C. over 2 hours using a dropping funnel. The reaction was continued at 35 ° C. for 2 hours to complete the amide oxidation reaction.

Subsequently, p-toluenesulfonic acid monohydrate 1
0.46 g was added, and azeotropic dehydration was performed under reduced pressure.
The dehydration ring-closing reaction was performed at 0 ° C. for 1 hour, at 110 ° C. for 1 hour, and then gradually returned to normal pressure at 135 ° C. for 4 hours. The reaction was carried out while separating the generated water from the system using a Dean-Stark azeotropic dehydration apparatus. Next, a total of 89% of chlorobenzene and then DMAc were recovered under reduced pressure.
Then, methyl isobutyl ketone (MIBK) 2200g
And dissolved. After cooling the solution to 60 ° C,
Baking soda and water 1 measured so that the pH of the aqueous layer becomes 5 to 7.
000 g was added for neutralization, followed by washing and liquid separation. Further, the mixture was washed twice with 1000 g of 15% saline at 60 ° C., separated, and then subjected to azeotropic dehydration under reduced pressure to remove salts by filtration. The filtrate was concentrated under reduced pressure, and finally 150 ° C / 5To.
After reaching the condition of rr, the product was taken out of the flask in a molten state, and 724 g of a light brown solid was obtained (yield 98.7).
%). From gel permeation chromatography (GPC), it was found that N, N′-bis (4-aminophenoxyphenyl) menthane bismaleimide was contained at 95% and the high molecular weight component was contained at 5%.

The properties of this product are shown below. Mass spectrum M + = 666 Melting point 96 to 98 ° C. 1H-NMR spectrum δ: 0.6 to 2.1 ppm (m, aliphatic), 2.8 p
pm (m, methine), 6.8 ppm (s, imide group), 6.9 to 7.4 ppm (m, aromatic) Infrared absorption spectrum: 1238 cm ^-1 (ether bond), 1712 cm ^-1 (Imide bond)

Synthesis Example 3 This synthesis example relates to a method for producing bis (4-aminophenoxyphenyl) dicyclopentanebismaleimide, which is a polymaleimide compound used in the present invention.
In Synthesis Example 2, YP-90 (trade name, manufactured by Yasuhara Chemical,
Reaction compound of dipentene and phenol, hydroxyl equivalent 1
Bis (4-aminophenoxyphenyl) menthane derived from DPP-600T
932.9 g of a DMAc solution of bis (4-aminophenoxyphenyl) dicyclopentane similarly derived from (trade name, manufactured by Nippon Oil Corporation) (concentration: 34.3%
And the same operation as in Synthesis Example 2 was performed.
7.4 g (98% yield) of bis (4-aminophenoxyphenyl) dicyclopentanebismaleimide 191.7
g (yield 97.4%) was obtained as yellow crystals.

The properties of this product are shown below. -Mass spectrum M + = 662, 1060-1H-NMR spectrum [delta]: 1.0 to 2.5 ppm (m, aliphatic), 2.7 pp
m (m, methine), 6.8 ppm (s, imide group),
6.6 to 7.3 ppm (m, aromatic) Infrared absorption spectrum: 1222 cm ^-1 (ether bond), 1712 cm ^-1 (imide bond)

SYNTHESIS EXAMPLE 4 This synthesis example relates to N, N'-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentanebismaleimide, a polymaleimide compound used in the present invention. The present invention relates to a method for producing an oligomer. 1
58.8 g of maleic anhydride in a 4-liter four-necked flask
And acetone (137.2 g) were charged and dissolved by stirring under a nitrogen stream. A dicyclopentane oligomer having 4- (4-aminophenoxy) -3,5-dimethylphenyl groups at both ends [DXP-L-9-1 (2, manufactured by Nippon Oil Co., Ltd.) while maintaining the temperature at room temperature to 35 ° C. Reaction product of 6-xylenol and dicyclopentadiene, hydroxyl equivalent 191 g
/ Eq) reacted with p-chloronitrobenzene and then the nitro group was reduced. Bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane is contained by 90% from GPC measurement. Amine equivalent 275
g / eq) of 150.0 g dissolved in 350 g of acetone was dropped into the flask over 2 hours. Stirring was continued for another 3 hours. Next, 16.6 g of triethylamine was added, and the mixture was stirred at room temperature for half an hour.
The temperature was raised to 0 ° C. After dropwise adding 72.4 g of acetic anhydride over 1 hour, the mixture was kept at the same temperature until the reaction was completed. After the completion of the reaction, the reaction mixture was added to 1000 g of pure water. The crystals were collected by filtration, washed with water, then with methanol, heated under reduced pressure and dried. The target compound was obtained as yellow crystals in a yield of 189.
4 g (97.9% yield) was obtained.

The properties of this product are shown below. -Mass spectrum M + = 718-1H-NMR spectrum [delta]: 1.0 to 2.5 ppm (m, aliphatic), 2.7 p
pm (m, methine), 6.8 ppm (s, imide group), 6.5 to 7.3 ppm (m, aromatic) Infrared absorption spectrum: 1220 cm ^-1 (ether bond), 1714 cm ^-1 (Imide bond)

Synthesis Example 5 In this synthesis example, N, N'-1,1-bis [4- (4-aminophenoxy) -5-t-butyl-2-methyl-2-imide, a polymaleimide compound used in the present invention, is used. [Methylphenyl] butanebismaleimide. 97.1 g of maleic anhydride and 226.5 g of acetone were charged into a 2-liter four-necked flask, and dissolved by stirring under a nitrogen stream. While maintaining the temperature at room temperature to 35 ° C, 1,1-bis [4- (4-aminophenoxy) -5-t-butyl-2
-Methylphenyl] butane 256.5 g in acetone 59
A solution of 8.5 g was added dropwise over 2 hours. Stirring was continued for another 3 hours. After adding 27.3 g of triethylamine and stirring at room temperature for half an hour, 0.95 g of nickel acetate was added and the temperature was raised to 40 ° C. After 119.9 g of acetic anhydride was added dropwise over 1 hour, the reaction was continued at the same temperature. After completion of the reaction, the reaction mixture was poured into 2.5 kg of water, and the crystals were collected by filtration. The crystals were washed with water, then with methanol, heated under reduced pressure and dried. Yield 306.1 g of the target compound as yellow crystals
(93.9% yield). This can be recrystallized from a mixed solvent of methyl cellosolve / isopropyl alcohol.

The properties of this product are shown below. Melting point 127 to 130 ° C., mass spectrum M + = 724 · 1H-NMR δ: 0.97 ppm (t, -CHCH 2 CH 2 C
_{H 3), 1.34 ppm (s} , t- butyl group), 1.
_{92 ppm (q, -CHCH 2 CH} 2 CH 3), 2.
17 ppm (s, methyl group), 4.13 ppm
_{(T, -CHCH 2 CH 2 CH} 3), 6.65 ppm
(S, imide group), 6.8 to 7.2 ppm (m, aromatic) Infrared absorption spectrum: 1219 cm ^-1 (ether bond) 1712 cm ^-1 (imide bond)

Example 1 This example relates to an example of preparing a cured product of a resin composition using the cyanate compound obtained in Synthesis Example 1.
The cyanate compound obtained in Synthesis Example 1 is melt-mixed with 0.1% by weight of zinc naphthenate, and methyl ethyl ketone is added to prepare a 50% by weight solution. After prepolymerization at 180 ° C, press at 200 ° C / 50kg / cm ² for 30 minutes,
By post-curing at 0 ° C. for 2 hours, a cured product having a thickness of about 2 mm was obtained.

Example 2 This example relates to an example of preparing a cured product of the cyanate compound obtained in Synthesis Example 1 and diglycidyl ether of tetrabromobisphenol A. 80 parts of the cyanate compound obtained in Synthesis Example 1 and diglycidyl ether of tetrabromobisphenol A (manufactured by Sumitomo Chemical Co., Ltd.
To 20 parts of Sumiepoxy ESB-400T (trade name), 0.3 part of zinc naphthenate is mixed, and methyl ethyl ketone is added to prepare a 50 wt% solution. After prepolymerization at 180 ° C, pressing was performed at 200 ° C / 50kg / cm ² for 30 minutes.
By post-curing at 5 ° C. for 5 hours, a cured product having a thickness of about 2 mm was obtained.

Comparative Example 1 This comparative example relates to an example of preparing a cured product of a resin composition using dicyanate of bisphenol A. A cured product having a thickness of 2 mm was prepared in the same manner as in Example 1 using dicyanate of bisphenol A.

Comparative Example 2 This comparative example relates to an example of preparing a cured product of a resin composition using bis (3,5-dimethyl-4-hydroxyphenyl) methane (bisphenol F) dicyanate. Using the above dicyanate, a thickness of 2 was obtained in the same manner as in Example 1.
mm cured product was prepared.

Table 1 shows the glass transition temperature and the dielectric constant of the cured products obtained in Examples 1 and 2 and Comparative Examples 1 and 2.

[0045]

[Table 1]

Examples 3 to 8 The cyanate compound obtained in Synthesis Example 1 was used at 140 ° C. together with zinc naphthenate as a curing agent.
To perform prepolymerization. The cyanate prepolymerized product and the polymaleimide compound obtained in Synthesis Examples 2 to 5, or N, N'-bis (4-aminophenyl) methanebismaleimide (produced by K-I Kasei Corporation), N, N '-2,2-bis (4-aminophenoxyphenyl) propanebismaleimide (trade name, MB80
00, manufactured by Mitsubishi Yuka Co., Ltd.) at a ratio shown in Table 2 together with a curing agent, and hot-pressed at 200 ° C./50 Kg / cm ² for 2 hours to prepare a cured product. Table 2 shows these physical property values. The numerical values of the mixing ratio in the table indicate parts by weight.

Comparative Example 3 Using a dicyanate compound of bisphenol A, Table 2
In the same manner as in Examples 3 to 8, a cured product was prepared. Table 2 shows these physical property values.

[0048]

[Table 2]

In Tables 1 and 2, the physical properties were measured by the following methods. -Glass transition temperature: Measured using a thermomechanical analyzer DT-30 manufactured by Shimadzu Corporation. -Dielectric constant and dielectric loss tangent: Capacitance values obtained by using a 4275A Multi-Frequency LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. to create electrodes on both sides of a cured product with a thickness of about 2 mm using metal paint. It was calculated and found.

[0050]

The cyanate resin composition of the present invention gives a cured product having excellent low dielectric properties and heat resistance (for example, a glass transition temperature of 180 ° C. or higher) that can withstand practical use.

Continued on the front page (72) Inventor Hisashi Watanabe 6, Kitahara, Tsukuba, Ibaraki Prefecture, Sumitomo Chemical Co., Ltd. (72) Inventor Mitsuhiro Shibata 6, Kitahara, Tsukuba, Ibaraki Prefecture, Sumitomo Chemical Co., Ltd. (72) Inventor Kanekawa Shuichi 6, Kitahara, Tsukuba, Ibaraki Prefecture Within Sumitomo Chemical Co., Ltd. (56) References JP-A-6-340028 (JP, A) JP-A-4-192489 (JP, A) JP-A-2-218751 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 C08L 79/00-79/08 CAPLUS (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] (1) The following general formula (1): (Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A is an alkyl group having 1 to 3 carbon atoms, and i is 0 to 3 A cyanate compound represented by the following integer value) or a prepolymer thereof and a curing agent as essential components: 2. A composition comprising a cyanate compound represented by the general formula (1) or a prepolymer thereof, a brominated epoxy compound or a prepolymer thereof, and a curing agent as essential components. A cyanate resin composition. 3. A prepolymer obtained by melt-mixing a cyanate compound represented by the general formula (1) according to claim 1 and a brominated epoxy compound alone or as a mixture with a curing agent, and a curing agent. The cyanate resin composition according to claim 2, wherein 4. A polymaleimide compound having a cyanate compound represented by the general formula (1) according to claim 1 or a prepolymer thereof, a curing agent, and two or more N-maleimide groups in a molecule or a polymaleimide compound thereof. A cyanate resin composition comprising a prepolymer as an essential component. 5. A polymaleimide compound having the following structural formula (2): [Wherein X is the following structural formula (3), (4), (5),
(6), (7) or (8) Embedded image Embedded image Embedded image (In the formula, n-Pr represents an n-propyl group.) Embedded image Is a group represented by The cyanate resin composition according to claim 4, which is a compound represented by the formula: 6. A cyanate compound represented by the following structural formula (9): A cyanate compound represented by the formula:
6. The cyanate resin composition according to 3, 4 or 5.