JPH05345748A - Poylamine and polymaleimide compounds - Google Patents

Abstract

PURPOSE:To obtain a new polyamine and a new polymaleimide compounds useful as intermediates for polymers excellent in balance between heat resistance and hygroscopicity. CONSTITUTION:The objective polyamide compound of formula I (R<1> is halogen, OH, phenyl, alkoxy or alkyl; R<2> is H or alkyl; R<3> is alkoxy or alkyl; l is 0-7; m is 0-3; the average number of recurring units is 0-10) and the objective polymaleimide compound of formula II (D is 2-24C bivalent structure having polymerizable unsaturated double bond). This new polyamine compound of formula I is obtained by condensing anilines with a naphthoyl compound. This new polymaleimide compound of formula II is obtained by imidating the new polyamine compound of formula I with an unsaturated dicarboxylic acid anhydride. The resultant polymaleimide compound can be used in a wide field such as adhesives, coatings, prepregs, laminated boards, molding and casting materials.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyamine compound and a polymaleimide compound which are useful as intermediates for heat-resistant polymers.

[0002]

2. Description of the Related Art Conventionally, a compound having an imide structure has been widely used industrially because it exhibits excellent heat resistance, electrical insulation, and dimensional stability of a molded product. For example, as a heat-resistant thermosetting resin used for electric / electronic component materials,
Polyimide-based resins, polyamine-modified polymaleimide-based resins, and the like are known and widely used for impregnating varnishes, laminated plates, molded products, and the like.

However, although these resins are generally excellent in heat resistance, they are not sufficient in hygroscopicity.
For example, in semiconductor encapsulation applications such as LSIs, ICs, and transistors, surface mounting of LSIs is performed, and the case where the encapsulant is directly immersed in a solder bath is increasing. In this case, since the sealing material is exposed to a high temperature of 200 ° C. or higher, the moisture absorbed in the sealing material expands and cracks easily occur.

Therefore, a material having a lower hygroscopicity and an excellent crack resistance is required for the resin sealing material,
A bismaleimide resin encapsulating material excellent in crack resistance under high temperature is under development, and for example, N, N'-4,
An encapsulating material using 4′-diphenylmethane bismaleimide can be mentioned. Further, recently, a bismaleimide resin having a biphenyl skeleton has been developed in order to improve hygroscopicity, which is a drawback of the bismaleimide resin. (Japanese Patent Laid-Open Nos. 62-167760 and 62-167777)

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to provide a heat-resistant polymer having physical properties having an excellent balance between heat resistance and hygroscopicity.

[0006]

The present invention comprises the following inventions. 1. General formula (1)

[0007]

[Chemical 3]

(Where R¹Are independent halogen sources
Child, hydroxyl group, phenyl group, alkoxy group having 4 or less carbon atoms
Or an alkyl group having 6 or less carbon atoms and R¹Is m
Are two or more, they are different even if they are the same in the same ring.
May be. R²Are each independently a hydrogen atom or carbon
An alkyl group having a prime number of 6 or less is shown. R³Each independently
Alkoxy group having 4 or less carbon atoms or alkene having 6 or less carbon atoms
Indicates a kill group, and R ³Is the same naphtha when l is 2 or more
They may be the same or different from each other in the len ring.
l independently represents an integer of 0 to 7 and the substitution position is naphth.
There is no particular limitation within the tarene ring. m is 0 independently
The average number of repeating units n is 0-10.
Show. ) The polyamine compound represented by.

2. General formula (2)

[0010]

[Chemical 4] (In the formula, each R ¹ is independently a halogen atom, a hydroxyl group,
A phenyl group, an alkoxy group having 4 or less carbon atoms or an alkyl group having 6 or less carbon atoms, and R ¹ may be the same or different in the same ring when m is 2 or more. R ^2's each independently represent a hydrogen atom or an alkyl group having 6 or less carbon atoms. R ³ independently represents an alkoxy group having 4 or less carbon atoms or an alkyl group having 6 or less carbon atoms, and R ³ may be the same or different in the same naphthalene ring when 1 is 2 or more. .. l's each independently represent an integer of 0 to 7, and the substitution position is not particularly limited in the naphthalene ring. m independently represents an integer of 0 to 3, and the average number of repeating units n is 0 to 10. D represents a divalent structure having a polymerizable unsaturated double bond and having 2 to 24 carbon atoms. ) A polymaleimide compound represented by:

The first invention relates to a novel polyamine compound which is a condensate of an aniline compound and a naphthoyl compound, which is useful as a raw material for synthesizing a polymaleimide compound.

The anilines used in the present invention include:
Aniline, toluidine, ethylaniline, propylaniline, butylaniline, xylidine, diethylaniline, ethylmethylaniline, ethylpropylaniline,
Ethylbutylaniline, methylpropylaniline, dipropylaniline, trimethylaniline, cyclohexylaniline, phenylaniline, chloroaniline, dichloroaniline, bromoaniline, dibromoaniline, fluoroaniline, chlorotoluidine, chloroxylidine,
Aminophenol, aminocresol, methoxyaniline, dimethoxyaniline, methoxymethylaniline, hydroxymethoxyaniline and the like (those having isomers include various isomers) can be mentioned. These anilines can be used not only alone but also as a mixture of two or more kinds.

Examples of the naphthoyl compound used in the present invention include 1-naphthaldehyde, 2-naphthaldehyde, hydroxynaphthaldehyde, methylnaphthaldehyde, methyl-1-naphthylketone and 2-methoxy-1.
-Naphthaldehyde, methyl-2-naphthyl ketone and the like and various isomers and derivatives thereof.

These naphthoyl compounds can be used not only alone but also as a mixture of two or more kinds.
Other carbonyl compounds may be mixed with these naphthoyl compounds to such an extent that the effects of the present invention are not impaired. Other carbonyl compounds include formaldehyde, acetaldehyde, acetone, benzaldehyde,
Examples include acetophenone, hydroxybenzaldehyde, aminobenzaldehyde, acrolein, crotonaldehyde, cinnamic aldehyde, glyoxal, 2,3-naphthalenedialdehyde, and various isomers and derivatives thereof.

The condensation reaction of these anilines and naphthoyl compounds is carried out by an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as acetic acid, p-toluenesulfonic acid or thioglycolic acid, an acidic catalyst such as Lewis acid, or an ion exchange resin. In the presence of 40-1
It can be carried out by a well-known method of post-treatment such as condensation at a temperature of 50 ° C., neutralization, washing with water, distillation of unreacted anilines and the like. When the target substance precipitates as crystals, the crystals may be filtered off, washed and dried.

The average number of repeating units n can be adjusted by the synthesis conditions such as the molar ratio of the aniline and the naphthoyl compound charged and the amount of catalyst. When n is 0, the melting point or melt viscosity of the target product becomes the lowest and it becomes easy to handle, but in consideration of the balance of physical properties of the cured product, a polyfunctional component may be contained, and n is 0 to 10, preferably 0 to 3. You can choose from a range of. When n exceeds 10, the melt viscosity of the target product becomes high, which is not preferable because handling becomes difficult. For use as a sealant, n is preferably 0 to 3, more preferably 0 to 1.5. On the other hand, when it is used by diluting it with a solvent such as for laminated plate use, the high melt viscosity does not necessarily become a practical obstacle, and therefore n is 0 to 0.
It can be appropriately adjusted and used in the range of 10 according to the purpose.

The second invention relates to a polymaleimide compound. The polymaleimide compound can be obtained by imidizing a condensate of the aniline of the first invention and a naphthoyl compound with an unsaturated dicarboxylic acid anhydride by a known method. For example, a known method of imidizing using a conventional dehydrating agent such as acetic anhydride, and JP-A 1-21
The method described in Japanese Patent No. 1563 can be applied.

Specifically, for example, 2 to 2.6 mol of an unsaturated dicarboxylic acid anhydride is used with respect to 1 mol of an aromatic diamine compound which is one of the polyamine compounds of the present invention,
Addition reaction is performed in a mixed solvent of an aromatic hydrocarbon solvent or a halogenated hydrocarbon solvent and an aprotic polar solvent, and 0.5 to 10 in the temperature range of 80 to 200 ° C. in the presence of an acidic catalyst.
The dehydration ring closure reaction can be carried out for a period of time.

As the aromatic hydrocarbon solvent, for example, benzene, toluene, xylene, etc. are used, and as the halogenated hydrocarbon solvent, for example, chloroform, 1,2-dichloroethane, chlorobenzene, etc. are used. As the aprotic polar solvent, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like can be used. In the mixed solvent, the mixing ratio of the aromatic hydrocarbon solvent or halogenated hydrocarbon solvent and the aprotic polar solvent is 50: 5.
It is about 0 to 99: 1. This mixed solvent is usually used in an amount of 1 to 10 times the weight of the raw materials.

After completion of the reaction, the reaction solution is added dropwise to a poor solvent to precipitate a desired product, and then the desired compound is obtained by filtering, washing and drying. Examples of the unsaturated dicarboxylic acid anhydride used in the present invention include maleic anhydride, itaconic anhydride, pyrosiconic anhydride, citraconic anhydride, dichloromaleic anhydride, and Diels-Alder reaction of these unsaturated dicarboxylic anhydrides and dienes. Mention may be made of products such as the Diels-Alder reaction products of maleic anhydride with cyclopentadiene, furan and terpinene. A polymaleimide compound having a D structure can be obtained by reacting these compounds with the polyamine compound.

[0021]

INDUSTRIAL APPLICABILITY The polymaleimide compound of the present invention is a polymaleimide compound having an excellent balance of heat resistance and hygroscopicity as compared with the conventional bismaleimide compound, and is used as an adhesive, a paint, a prepreg, a laminate, a molding. It can be used in a wide range of fields such as materials and casting materials.

[0022]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. The evaluation of the cured molded product is as follows.・ Glass transition temperature: Thermomechanical analyzer (SHIMADZ
It was measured using UDT-30).・ Water absorption rate (measure of hygroscopicity): Constant temperature and humidity chamber (TABAI
PR-2) was used to measure the weight change under the condition of 85 ° C./85% RH.

Example 1 Synthesis of diamine 892.8 g (9.60 mol) of aniline in a 3 liter four-necked flask equipped with a stirrer, thermometer and condenser.
1-naphthaldehyde 187.2 g (1.20 mol)
Then, 45.0 g (0.44 mol) of concentrated hydrochloric acid was charged, the reflux temperature was raised to 110 ° C., and the temperature was kept for 6 hours. After the reaction was completed, the internal temperature was 60 ° C., and a 20% aqueous sodium hydroxide solution
3.2 g (0.67 mol) was added while paying attention to the heat of neutralization, and the mixture was stirred for 1.5 hours to precipitate crystals. After cooling to room temperature and separating the crystals by filtration, the crystals are washed twice with 300 g of water and twice with 500 g of toluene, and dried under reduced pressure at 80 ° C. to give 180.5 g of white crystals (referred to as P-ANNA). Obtained. The melting point of this product is 225-
232 ° C., amine equivalent is 164 g / eq. Met. When the infrared absorption spectrum (KBr tablet) of this diamine was measured, it was 3200 to 3400 cm ⁻¹ (amino group),
Characteristic absorption was observed near 790 cm ^-1 (α-substituted naphthalene). Nuclear magnetic resonance spectrum, ¹ H-NMR
(Chloroform d ₃ ) δ (ppm) is 3.57 (s4
H), 6.06 (s1H), 6.78 (dd8H),
It was 6.95 to 8.02 (m7H).

Example 2 Synthesis of Bismaleimide 23.5 g of maleic anhydride (0. 0%) was placed in a 500 ml four-necked flask equipped with a stirrer, a thermometer and a condenser.
24 mol) and 118 g of toluene were charged and dissolved by stirring.
To this solution, a solution prepared by previously dissolving 32.4 g (0.10 mol) of P-ANNA in 97.2 g of N-methyl-2-pyrrolidone was added dropwise at an internal temperature of 20 ° C. over 2 hours, and the temperature was further kept for 2 hours. Then, 0.95 g (0.005 mol) of p-toluenesulfonic acid monohydrate was added, and the internal temperature was 120 ° C.
The temperature was raised up to and reacted for 10 hours. During this time, water produced by the reaction was continuously distilled out of the system. After completion of the reaction, under reduced pressure 8
Toluene was distilled off at 0 ° C. to obtain a resin liquid. This resin liquid
It is dropped into 1000 g of water which is being stirred at a high speed, the deposited precipitate is separated by filtration, washed with 500 g of water 5 times, and dried under reduced pressure at 60 ° C. to obtain a target yellow powder (designated ANNA-M). 36.0 g was obtained. The softening point of this is 140-
It was 145 ° C. The infrared absorption spectrum (KBr tablet) of this maleimide was measured to be 1710 cm.
^-1 (derived from the imide ring) showed characteristic absorption. Nuclear magnetic resonance spectrum, ¹ H-NMR (chloroform d ₃ ) δ
(Ppm) is 6.33 (s1H), 6.80 (s4)
H), 6.70 to 7.97 (m15H).

Reference Example 1 and Comparative Reference Example 1 ANNA-M and N, N'-4,4'-diphenylmethane bismaleimide (referred to as BMI) were used to evaluate a cured molded article. Glycidyl ether compound of orthocresol novolac as epoxy resin (trade name: Sumiepoxy ESCN-195XL, Sumitomo Chemical Co., Ltd.)
Phenol novolac (trade name: Tamanor 759, manufactured by Arakawa Chemical Industry Co., Ltd.) as a curing agent, triphenylphosphine as a curing accelerator, fused silica as a filler (trade name: FS-891, Electrochemical Industry ( Co., Ltd.),
Carnauba wax as a release agent and a coupling agent (trade name: SH-6040, manufactured by Toray Dow Corning Silicone Co., Ltd.) were blended in the amounts shown in Table 1, heated and kneaded with a roll, and press-molded. Further, post-curing was performed in an oven at 180 ° C. for 5 hours to obtain a cured molded product. The glass transition temperature and water absorption of this cured molded product were measured, and the results are shown in Table 1. It can be seen from Table 1 that the polymaleimide compound ANNA-M of the present invention has a good balance between heat resistance and hygroscopicity.

[0026]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C08G 73/02 9285-4J // C08F 22/40 MNE 7242-4J C08G 73/12 NTH 9285-4J (72) Inventor Shinji Akiba, 6 Kitahara, Tsukuba, Ibaraki, Sumitomo Chemical Co., Ltd. (72) Inventor, Hiroshi Shiomi, 6 Kitahara, Tsukuba, Ibaraki, Sumitomo Chemical Co., Ltd. (72) Inventor, Mitsuhiro Shibata, Kitahara, Tsukuba, Ibaraki 6 Sumitomo Chemical Co., Ltd.

Claims (2)

[Claims] 1. A general formula (1): (In the formula, each R ¹ is independently a halogen atom, a hydroxyl group,
A phenyl group, an alkoxy group having 4 or less carbon atoms or an alkyl group having 6 or less carbon atoms, and R ¹ may be the same or different in the same ring when m is 2 or more. R ^2's each independently represent a hydrogen atom or an alkyl group having 6 or less carbon atoms. R ³ independently represents an alkoxy group having 4 or less carbon atoms or an alkyl group having 6 or less carbon atoms, and R ³ may be the same or different in the same naphthalene ring when 1 is 2 or more. .. l's each independently represent an integer of 0 to 7, and the substitution position is not particularly limited in the naphthalene ring. m independently represents an integer of 0 to 3, and the average number of repeating units n is 0 to 10. ) The polyamine compound represented by. 2. A general formula (2): (In the formula, each R ¹ is independently a halogen atom, a hydroxyl group,
A phenyl group, an alkoxy group having 4 or less carbon atoms or an alkyl group having 6 or less carbon atoms, and R ¹ may be the same or different in the same ring when m is 2 or more. R ^2's each independently represent a hydrogen atom or an alkyl group having 6 or less carbon atoms. R ³ independently represents an alkoxy group having 4 or less carbon atoms or an alkyl group having 6 or less carbon atoms, and R ³ may be the same or different in the same naphthalene ring when 1 is 2 or more. .. l's each independently represent an integer of 0 to 7, and the substitution position is not particularly limited in the naphthalene ring. m independently represents an integer of 0 to 3, and the average number of repeating units n is 0 to 10. D represents a divalent structure having a polymerizable unsaturated double bond and having 2 to 24 carbon atoms. ) A polymaleimide compound represented by: