JPH03162450A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition, excellent in heat resistance, processability and electrical characteristics and suitable as printing circuit boards, molded products, etc., by blending a specific polyazomethine with specified bismaleimide. CONSTITUTION:A thermosetting resin composition obtained by blending (A) a polyazomethine having recurring units expressed by formula I (Ar1 and Ar2 are bifunctional aromatic group) with (B) an unsaturated bismaleimide compound expressed by formula II (Ar3 is bifunctional aromatic group; D and D' are bifunctional organic group having unsaturated bond) in an amount of 0.05-5mol, preferably 0.1-2mol based on 1mol recurring units expressed by formula I.

Description

Detailed Description of the Invention (a) Industrial Application Field The present invention is used for manufacturing printed wiring boards or shaped products that have excellent heat resistance, good workability, and excellent electrical characteristics. Thermosetting? Regarding flf oil.

(b) Advanced technology In recent years, the usage conditions for electrical/electronic equipment, parts, automatic wiring, and aviation equipment have become more severe.For example, printed wiring boards have become more multilayered and denser There is a tendency for these materials to be implemented in practical packaging, requiring improvements in heat resistance and dimensional stability, as well as lower dielectric constants. At present, fat materials have particularly excellent heat resistance and shapeability. For binding purposes, addition-polymerizable M aromatic maleimide resins, which do not produce volatile substances during curing, have come into widespread use. Various types of aromatic maleimide resins have been developed, and have been put into practical use by improving shapeability, moisture resistance, strength, etc. by using maleimide alone or by modifying it with other thermosetting resins such as polyamines (for example, Tokuko Showa 4 6-2
3250).

However, this product has poor dimensional stability and cannot meet the demands for higher density, higher multilayer, smaller size, and higher height of moxibustion equipment.

Therefore, the following thermosetting resin III't molded product made of polyazomethine has been proposed. That is, TV 7
In reacting taraldehyde, 3.4-diamino/no-7enyl ether, and p-7 enylene diamine conductor as main raw materials with a predetermined compounding agent, a predetermined amount of diamine component, for example, N- Methyl pyrrolidone (NM
P), hexamenal phosphor triacetate (HMP)
By dissolving dialdehyde in A), adding dialdehyde as a solution, and reacting, a heavy polymer (polymer) is obtained.

In this case, metal halides such as lithium chloride, calcium chloride, etc. are added for solubilization (vf
3-234030).

(c) Problems to be Solved by the Invention However, impurities such as metal ions remain in a certain shaped product obtained in this way, which particularly affects the electrical properties of the product, so its use is extremely limited. Ru.

That is, in general, this thermosetting resin is particularly suitable for electrical and electronic applications.
! It is often used as an insulating material for devices, printed wiring boards, and laminates, but the presence of lithium ions, calcium ions, and chlorine ions can cause the electrical properties to deteriorate. There are problems such as corrosion of electrical conductors in devices, printed wiring boards, etc., and therefore, despite the fact that poly-7zomethine has excellent heat resistance, it is not put into practical use.

In addition, recently, fluorine-containing polyimide has attracted attention as a material with low electrical conductivity. For example, it is known as Sixef, but it has a fatal drawback that it cannot be used in electrical and electronic fields because it is soluble in solvents. Also, this item has a high ratio and is not suitable for inorganic materials or metals.
There are many problems that need to be solved, such as poor adhesion and poor solubility in solvents, which limits its application to varnish paints, and inferior heat resistance compared to condensed polyimides. I cannot say that it is being done enough. Also, this product is heat resistant and suitable for electronic parts and electrical equipment! F
t' Required dimensional stability C coefficient of linear expansion), thermal decomposition temperature, Fuss transition temperature, solvent resistance (it}17 cleanability)
However, there was a problem in that it was difficult to balance properties such as adhesive strength to metals, and it was difficult to achieve sufficient performance and reliability of the applied products. The present invention has been completely IR-developed in order to solve the above technical problems, and involves making specific bismaleimide contained in Nede's poly7zomethine and reacting them by heat curing to produce a specific boriazomethine. By denaturing, heat resistance and dimensional stability can be improved, and the temperature can be lowered. It is an object of the present invention to provide a thermosetting resin all-purpose material that can increase the Ti ratio, thereby enabling high multilayering and high-density packaging of electronic components.

(d) Means for Solving the Problems In order to achieve the above objects, the resin composition has the general formula [A] thermosetting -4CH-^rl CH=N-^r2-N half [
In the boriazo/chin having repeated undulations consisting of A1,
A thermosetting resin composition containing the general formula [B].

(However, Ar+ and V A r 2 and Ar. represent a divalent aromatic group, D and D′ are organic groups having a divalent unsaturated bond, and Art and Arz and D and D′ are the same. (However, they may be different.) In the above general formula [A], examples of Ar are ζ, etc., and as Ar2, ? R' is an alkylene group, -C11■--C(
CIl1) 2 s par 7 tl + loal ~ ren group, 7
At least one inhibitor selected from the group consisting of anole and lene groups
is free, and X and Y are at least one group selected from an alkyl group, a 7-alkynole group, a 7-chain group, a chloro group, and a promo group. Also, n is O or 1, integer is an integer from O to 4, and l is 0
It is an integer of ~4, and is particularly preferable as R' because a low current conductivity material can be obtained.In addition, in the general formula [A], other examples of Arl are (113?ReSO■Order, *S *, 1 ◎ 1 Sow- ◎ 1. The thermosetting resin composite of the present invention can be obtained by the following method.

That is, first, boriazomethine or its copolymer used in the present invention can be thermally polymerized from suitable monomers, preferably under anhydrous conditions in an inert atmosphere.

For example, the raw material noamine (ll2N-8rz-MH2)
and noaldehyde 1 or its derivatives, noacetal, diketone (hereinafter collectively referred to as noaldehydes)] (Z.
．． 22 (hydrogen, methyl group, ethyl group) are combined in approximately equimolar amounts in a reaction vessel. Inert A-form (N2〃s, etc.)
Dehydrated solvent (NMP, DMAc, etc.) while introducing
(so that the monomer is 20-40 wt%)
and stir at room temperature for several hours. Next, in order to remove by-products (water, methanol, etc.), the temperature is heated for 7 to 10 hours, and azeotropic dehydration is carried out by adding a solvent such as benzene or toluene using Dean-Stark's azeotropic dehydration method. do. A predetermined amount of a substance represented by the general formula [B1, which will be described later, is added to the obtained polymer solution, which is then desolubilized (by heating, hot air, etc.) and heated. Alternatively, the polymer may be poured into a non-solvent such as water or methanol, washed and dried, and then mixed with a predetermined amount represented by the general formula [B].

This polycondensation reaction can be obtained by solution polycondensation using approximately equal moles of the corresponding cyamine and dialdehyde.
It can also be obtained by bulk melt polycondensation. In this solution polycondensation, examples of solvents used include N-methynole-2-pyrrolidone (NMP), di/tylsulfoxide (DMSO), N. N-nomethylacetamide (DMAc), N,N-diethylacetamide (DEAc), N. N-Nomethylformamide (
Aprotic polar cutting such as DMF) is used, and depending on the composition, general-purpose non-polar solvents such as toluene and xylene are also ITr-soluble.

In this case, it is preferable to remove the raw water by azeotrope, but since the raw water is removed when the properties are improved by heat curing treatment, it is not necessary to remove the raw water.

In the present invention, the average degree of polymerization of the boriazomethine used can be expressed by the intrinsic viscosity η (g/d/);
That's all, special 1:0. The limiting viscosity η (g/df) is preferably within the range of 0.2-2 g/d (l).
If it is less than 2 g/d1, even if the heat treatment described below is applied, the effect will be small and the film shapeability will be poor. On the other hand, if it exceeds 2 g/d1, the solubility in the solvent will be poor. If the degree of polymerization becomes too large, the viscosity of the solution becomes abnormally high, which may make handling inconvenient, which is not desirable.

However, although there is no particular upper limit to this limiting viscosity η (g/df), poly7zomethine generally has poor solubility in solvents, and as the degree of polymerization increases, the solution viscosity becomes abnormally high, making it difficult to handle. Although it is often inconvenient, in the present invention, specific monomers (A r
When at least one of 1 and A r2 is fluorine-based), even if the polymer has a high degree of polymerization, it has excellent solubility in solvents and is easy to handle. In this case, especially when lowering the viscosity is desired, the ends of the polymer may be blocked with a small amount of blocking agent.

For example, aniline, 4-canoleboxybenzaldehyde, benzaldehyde, 2,3,4,5. 6-hebuta-7-rolobenzaldehyde, 3-7-rolomethylbenzaldehyde, 4-tri-7-rolomethylbenzaldehyde, and 4-7-/acetanilide are used.

The above boriazomethine is a solvent, such as NMP, DMSO1
DMAc. It is soluble in aprotic oleaginous solvents such as DEAc and DMF, and in some cases general-purpose non-polar agents such as toluene and xylene, and also in mixed solvents of these. Examples of diamines used in the present invention include those having the general formula [AI] with Ar2 in the molecular skeleton. In addition, the thermosetting resin film of the present invention is obtained by containing an unsaturated bismaleimide represented by the general formula [Bl] in the above polyazomethine.

(However, Ar) represents a divalent organic group like Ar2,
D and D゜ are organic groups having a divalent unsaturated bond, and D
and D' may be the same or different. ) Specific representative examples of this unsaturated bisimide include the bismaleimide of the above-mentioned 7mine.

Such an unsaturated bismaleimide can be obtained by a conventionally known method, and is obtained by reacting an unsaturated nocarboxylic acid anhydride with a noamine.

Suitable examples of this unsaturated nocarboxylic acid anhydride include (
a) Maleic anhydride or its derivatives, such as nomethyl maleic anhydride, diisoprobyl maleic anhydride, dichloromaleic anhydride, and the like.

(b) tetrahydroheptalic anhydride or a derivative thereof, such as methyl tetrahydroheptalate; (e) nadic anhydride or a derivative thereof, such as methyl nadic anhydride, oxynanocic anhydride, nomethoxynadic anhydride;
Examples include hexachloronadic anhydride. Further, examples of other unsaturated bisimides include the following.

Further, examples of noamines used here include those having Ar= in the molecular skeleton in the above general formula FBI.

In the present invention, boriazomethine represented by general formula [A] and general formula [Bl'? The blending ratio of the unsaturated bisimide compound shown in l' is not particularly limited, but
For 1 mole of repeating units of general formula [A], general formula [B]
The unsaturated bisimide compound represented by is 0.05 to 5.0
It is preferably within the molar range, particularly 0.1 to 2.
The most desirable range is 0 mol. If the amount of the unsaturated bisimide compound represented by the general formula [B1 is less than 0.0 mol, the solubility in solvents will be poor and it will be difficult to handle, and even if the curing reaction treatment described below is performed, sufficient properties will not be obtained. Therefore, extremely high temperature and curing time are required, which is undesirable as it causes oxidative deterioration of the tree bark and increases the yJ electric rate. This is not desirable because it becomes brittle and has poor heat resistance. The thermosetting resin composition of the present invention can be blended as a resin component and supplied as is, but the blend can be heated to 200°C.
It may be supplied in the form of a so-called pre-bolimer which has been pre-reacted at the following temperature. It may also be supplied in solid form such as powder. In the case of the present invention, even without special prepolymerization, a sufficiently low coefficient of linear expansion is achieved in the curing reaction described below, and high strength and low α? I! have characteristics.

In the present invention, the thermosetting resin composition can be dissolved in a suitable solvent, so-called varnish, and can be supplied as a varnish that has room salt storage stability, that is, a long pot life and good storage stability. Examples of methods for curing the thermosetting resin of the present invention include DMSO, DMF, DMAc%NMP, dichloroethylene, tetrachloroethylene, chlorobenzene, nochlorobenzene, cyclohexanone, dioxane, and alkylated aromatic hydrocarbons. , MIBK. The composition can be dissolved in a solvent such as MEK, cast, the solvent evaporated, and cured. At this time, organic peroxides with low electric current such as not-t-butyl peroxide, norauryl peroxide,
Nocumyl peroxide, t-butyl cumyl peroxide, and t-butyl peroxide may be used in an amount of 0.01 to 5% by weight based on the total amount. It is also possible to use curing accelerators other than 8113 Pa compounds or additives that favorably affect curing.

The curing temperature is 10% in an air atmosphere or in an inert gas atmosphere.
A network-bonded insoluble and infusible plastic can be produced by heating at 0 to 300°C for several minutes to several tens of hours.

Thus, the general formula [A] + CH-8r+-C}I=N-8r, -N+
Boriazomethine having an a9 repeating unit consisting of [A] and thermosetting N{ffl having a repeating unit consisting of the general formula [C] are obtained. (However, Ar+, Ar2, and Arz all represent divalent aromatic groups, D and D′ are organic groups having a divalent unsaturated bond, and Ar2 and Ar3 and D and D′ may be the same. (They may be different.) This network-bonded infusible material can generally be made into a shaped body, a planar structure, a laminate, or a bonded body at the same time as its manufacture. In this case, it is possible to add to the curable composition the additives customary in the curable plastics industry, fillers, plasticizers, pigments, dyes, mold release agents, flame retardants.

As the above-mentioned filler, for example, lath fiber, mica, quartz, kaolin, colloidal silicon dioxide, or metal powder can be used, and as the mold release material, for example, potassium stearate can be used. The shape is in air or directly under an inert atmosphere, 1 to 2 0
This can be done by heating at 100-300°C, especially 170-250°C, for several minutes to several tens of hours at a pressure of 0 kg/cm. The shaped body thus produced already has sufficient W1 mechanical strength. and outside the press 200-280
It can be completely cured in an oven at ℃. When a prebolimer is first produced from the curable M-Kaimono, it can also be ground into a fine powder and used as a surface protection agent after the vortex sintering process.

The thermosetting resin composition can be dissolved using an appropriate solvent and used for the 9I construction of the laminate. In this case, this resin solution is impregnated into a porous planar structure, such as a woven fabric, a fiber mat, a fiber wreath, a glass fiber mat, or a lath fiber woven part, and the solvent is removed by a drying process. In a press, especially at 120-250℃, 5-200kg/
Further curing is performed at a pressure of am2. It is also possible to pre-cure the laminate in a press and to post-cure the resulting product in an oven at 200-300 DEG C. until optimum use properties are reached.

In the present invention, in particular, A'1, A in the general formula rAI
Containing a per7fluoro7rukylene group or a heptafluorinated aromatic group in at least one group of r2 may result in an extremely low electrical current, and may also cause by-products (such as water) to be generated during the curing process. It is extremely useful because it has good cracking resistance when processing through-holes when used as a substrate and when immersed in a hanging solution.

Suitable examples of the above-mentioned per-7-fluoroalkylene group or heptafluoroaromatic method include:

(e) Effect The thermosetting 1111It composition of the present invention has the above structure, and a portion of the polyazomethine is atm! It improves the solubility of the composition, making it easier to impregnate glass cloth, etc. Also, by incorporating the bismaleimide, it becomes insolubilized by heat curing, so it has the effect of improving solvent resistance.

Moreover, this thermosetting resin composition is heated at a specific temperature (approximately 120°C
I-1:. ) The insolubilization reaction does not proceed unless the above conditions are met, so it is stable for a long pot life, and has low hygroscopicity, so it has good electrical properties and good corrosion resistance.Furthermore, this heat Since the curable resin composition does not use low-molecular substances, it has strength, flexibility, and good electrical properties.

(f) Examples Next, the present invention will be described in detail based on Examples, but the present invention is not limited thereto.

Example 1 Taraldehyde and BAPF were charged into a flask at a molar ratio of IN1, and dehydrated NMP was added under a stream of N2 gas to give a monomer concentration of 20% by weight. After stirring at room temperature for 4 hours, 20 parts of toluene and 100 parts of solvent were added, the temperature was raised to 150°C, and the by-filtrate water was completely removed by azeotropy. An NMP solution of polyazomethine was obtained.

NMP solution of poly7zomethine ([k]recl=0
．． 48, Kame weight average molecular fi 86,000) was obtained. On the other hand, 77 tons of maleic anhydride 33 moZ at room temperature
Dissolve BAPF0.05 ring o1 in this and add ace1
The solution dissolved in the tube 1008 is slowly added dropwise. To this, add 0.02 g of cobal acetate and 0.2 g of magnesium oxide, and stir well.

Further, 2.4 g of triethylamine and 13 g of acetic anhydride are added dropwise, and the mixture is stirred overnight.

Pass through a glass filter, disperse in water and acetone, and wash. Next, 27 g of bismaleimide was obtained by drying under reduced pressure.

Then, the above polyazomethine NMP78810)?
Then, the above bismaleimide (BAPFMI) was added to Hori 7.
0.67 mol per 1 structural unit of zometine was added and mixed well at room temperature. Apply this solution uniformly and apply 100%
Put it in the dryer at 150°C for 2 hours, and then put it in the dryer at 150°C for 2 hours.
It was dried at 250°C for 12 hours. Gradually cool down to a coating thickness of 7.
5 μm of water was obtained.

The 5% weight loss thermal decomposition temperature of this film is 1'd,j! 7 Las transition temperature Tg, M expansion coefficient (1, NMP resistance is shown in Table 1.

Examples 2 to B and Comparative Examples 1 to 5 Various films were prepared in the same manner as in Example 1 using the polymers and bismaleimide shown in Table 1.

The characteristic results are shown in Table 1.

Comparative Example 6 8 parts by weight of 3.4-diami-7 di-7enyl ether in NMp
2stliff5, hexamethylphosphortriaside 2
It was dissolved in a mixed system of 5 parts by weight of anhydrous lithium chloride and 5 parts by weight of anhydrous lithium chloride while flowing nitrogen. Next, 5.36 g of yst' teraldehyde was gradually added and mixed, and the mixture was allowed to react at room temperature for 48 hours. After the reaction was completed, it was poured into water, and the precipitated yellow powder polymer was filtered off. Subsequently, water washing was repeated, washed with methanol, and dried to obtain boriazomethine [poly(nitrilo-3-7 enyl ether-4'-7 enylene nitrilomethylidene-1.4-7 enylene methylidene) 11
2.3 parts were obtained.

The characteristic results are shown in Table 1.

(Margins below) From the results shown in table fjS1, the examples have better heat resistance and solvent resistance, lower #I expansion coefficient, lower dielectric constant, and better adhesion than comparative examples. It is recognized that the power is great. (F1) Effect of the invention In the thermosetting resin composition of the present invention, a specific bismaleimide is contained in a specific boriazomethine, and the specific bismaleimide is reacted with the heat curing to modify the specific polyazomethine. In addition to improving the properties and dimensional stability, it is also possible to lower the dielectric constant, which has the effect of making it possible to increase the number of layers and high-density packaging of electronic components.

Procedural amendment (voluntary) Plain 2 years February 1 day 1.Display of the incident 2. Name of the invention 3. Person who makes corrections Relationship with the incident shelter name 4. Agent address Patent application No. 1-303600 Thermoset bamboo silk fabric

Claims (2)

[Claims] (1) General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[A] Polyazomethine having a repeating unit consisting of the general formula [B] ▲Mathematical formulas, chemical formulas, tables, etc.▼・...[B] A thermosetting resin composition containing. (However, Ar_1, Ar_2, and Ar_3 are all divalent aromatic groups, D and D' are organic groups having a divalent unsaturated bond, and Ar_2 and Ar_3 and D and D' are the same or different. is also good.) (2) The thermosetting resin composition according to claim 1, wherein at least one of Ar_1 and Ar_2 in the general formula [A] is a perfluoroalkylene group or a fluorinated aromatic group.