JPS59179668A - Solvent type varnish - Google Patents

Abstract

PURPOSE:To provide the titled varnish having excellent electrical insulating properties, heat resistance, adhesion and room temperature flow characteristics, by dissolving a resin compsn. consisting of a resin of bismaleimide with a triazine resin and an epoxy resin in a specified solvent. CONSTITUTION:10-90wt% resin (A) composed of a bismaleimide of formula I (wherein Ar1 is a bivalent arom. group), a diisocyanate of formula II (wherein Ar2 is Ar1) and a triazine resin of formula IV, having cyanate groups at its terminal and contg. triazine rings of formula III formed by the cyclopolymerization of three or more diisocyanate molecules, and 90-10wt% epoxy resin (B) contg. an average of at least three epoxy groups per molecule and having an MW of 500 or above, are dissolved in a diethylene glycol monoalkyl ether acetate or diethylene glycol alkyl ether solvent, and reacted at 80-120 deg.C for several hr.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention has excellent electrical insulation, heat resistance, and adhesion, as well as good cold fluidity as a varnish, and its workability has been significantly improved. The present invention relates to a solvent-based varnish suitable for electrical insulation and various passivation applications.

[Technical background of the invention and its problems] In recent years, as electric and electronic equipment becomes more compact and has higher performance, electrical insulating materials are also required to have excellent heat resistance. BACKGROUND OF THE INVENTION Polyimide resins, polyamide-imide resins, and the like with excellent mechanical and electrical properties have been developed and are now being widely used in electrical and electronic devices.

However, these resins are different from so-called solvent-free types such as unsaturated polyester resins and epoxy resins.
IC, which is a solid with a high melting point and glass transition point when used alone,
During processing, it is necessary to mold the material by heating and pressing, or to use it by dissolving it in a solvent. In this case too, ordinary organic solvents do not dissolve in 10 minutes! However, non-prone polar solvents such as N-methyl-2-pyrrolidone and N,N-dimethylamide must be used mainly, resulting in extremely poor processability and complicated processing operations. There was a drawback. Furthermore, in the case of a varnish using a solvent system as mentioned above, when applied by screen printing, etc., the screen emulsion may be dissolved, which is undesirable, and the varnish may have bad odor, roughness, and poor adhesion to various paper substrates. There was a drawback.

On the other hand, unsaturated polyester resins and epoxy resins do not require solvents during the molding process, so they do not cause problems due to solvent volatilization, but on the other hand, they have the disadvantage that the heat resistance and insulation properties of processed molded products are inferior. Therefore, the field of use has been limited. Also,
Traditionally, N.

J: On thermal polymerization of N''-substituted maleimide compounds:
Although it is known that a resin with excellent heat resistance can be obtained by using this method, this resin is extremely brittle and easily cracks during cold Ul-heating cycles, so it is not practical as it is. Recently, however, heat resistance and flexibility have been added to this resin!
-j, varnishes have been developed that use a combination of N,N--substituted maleimide compounds, vinyl 1Jff1, epoxy resin, unsaturated polynisdel, N-substituted maleimide compounds, etc. The substituted maleimide compound itself is solid at room temperature, and has poor affinity with solvents and dissolves easily, so N is not used in such varnishes.

The disadvantage was that the N''-substituted maleimide compound was prone to crystallization.Furthermore, this type of varnish had a high viscosity;
Since it is necessary to impart fluidity by heating to a high temperature during processing, there is a drawback that processing operations are extremely complicated.

[Purpose of Defense j The purpose of the present invention was to eliminate such conventional drawbacks. The purpose is to provide a solvent-based varnish that is not bulky, toxic, and odor-free.

[Summary of the Invention] The present invention was developed as a result of intensive research to achieve the above object.
We have discovered a solvent-based varnish that overcomes the above-mentioned drawbacks and is excellent for electrical insulation and various passivation applications with the composition described below.

That is, the present invention provides a resin composition consisting of (a) a resin containing bismaleimide and a triazine resin monomer as main components, and (j) a J boxy resin, and a resin composition consisting of diethylene glycol monoalkyl ether acetate or diethylene glycol. This is a solvent-based varnish characterized by being dissolved in a sialygyl ether solvent.

(a) The resin mainly composed of bismaleimide and a triazine resin monomer used in the present invention is a bismaleimide represented by the general formula, and a resin represented by the general formula N=C-0-Ar 2-O-C=N. A dicyanate having a tri-7nodine ring formed by cyclopolymerization of three or more molecules of dicyanene = 1 to 3 molecules in the molecule and having a cyanate group (N = (,0-) at the end of the molecule, for example, having the following structural formula) (However, Ar , Ar 2 represent the same or different divalent aromatic M groups.) Such resins include, for example, BT resin (trade name: Mitsubishi Gas Chemical Company). ).

The epoxy resin (b) used in the present invention includes, for example, the following diepoxydes of bispots and nols. Epikote 8 manufactured by Shell Chemical Co., Ltd.
27,828,834,1001゜1002.1004
, 1007.1009, Dow Chemical Company DER33
0,331,332°334.335,336,337
,660°661.662,667.668,669,
Ciba JJ-(Key Corporation tJ7 Raltai 1-(Araldi)
te) GY250.260.280.6071,6
084゜6097.6099, J ones D
Abney Ep! -Re5510, 5101, Ebikuron 810, 1000, 1 manufactured by Irunichi Mizu Ink Chemical Industry Co., Ltd.
010°3010 (all of the above are product names).

Furthermore, in the present invention, the adhesive strength of the varnish can be further improved by using, for example, a novolac epoxy resin having an average number of epoxy groups of 3 or more as the epoxy resin. As the novolak epoxy resin to be used, one having a molecular weight of 500 or more is suitable. Examples of such novolac epoxy resins include the following. Araldai 1 manufactured by Ziba Geigy
~(Araldite) EPN 1138. 11
39, ECN1273, 1280.1299, Dow Chemical Company EN431, DEN438, Shell Chemical Company Epikote 152.154
, Union Carbide ERR-0100゜ERR
B-0447, ERLB-0448, etc.

(a) Bismaleimide and 1 to lyazine resin 7mer
It is desirable that the blending ratio of the resin whose main component is 10:90 to 90:210 (weight ratio) and the epoxy resin (b) is in the range of 10:90 to 90:210 (weight ratio). (a) If the blending ratio of the resin whose main components are bismaleimide and triazine resin upper layer is less than the above range, the softening temperature of the resulting varnish coating will be low, resulting in poor adhesive strength at high temperatures. ,
On the other hand, if the amount exceeds the above range, the flexibility of the resulting varnish coating will decrease, which is not preferable. Therefore, it is limited to the above range.

(a) Bismaleimide and l-lyazine resin tops
When blending the resin whose main components are C-b and the epoxy resin of (, b), it is better to add these resins to a common solvent at the same time and dissolve them, but first add the latter to the solvent. It is desirable to dissolve the former after dissolution.

Furthermore, the organic solvent used in the present invention is a di-1-bulene gelylcol monoalthedel solvent, which is used as a general ink solvent and does not attack the screen emulsion, is non-toxic, and has little odor. It is possible. Examples include diethylene glycol monobutyl needle acetate, diethylene glycol monobutyl needle acetate, diethylene glycol dimyl ether, diethylene glycol dibutyl ether, and the like. These solvents can be used alone or in combination of two or more.

In addition, by dissolving the resins of (a) and (b) above in a solvent and then heating and reacting them at a temperature range of 80°C to 120°C for several hours, cyanate groups can be formed with each other, cyanate groups and epoxy groups, and cyanate groups and bis The viscosity and molecular weight of the varnish can also be adjusted by a partial reaction with maleimide. Furthermore, the varnish of the present invention may contain a known curing catalyst in addition to the above-mentioned necessary components. As a curing catalyst, for example, a polymerization initiator J3 of 1B such as benzoyl bar Δ kylyide, dicumyl peroxyloid, ditertiary butyl peroxylide, azobisisobutylyl, etc., and as a promoter, tertiary amines and imidazoles are used. , organic metal salts, and chlorides are used as appropriate.

In addition, if necessary, fillers made of inorganic powders such as silica powder, mica powder, and carbon powder, or resin powders such as polyimide powder, polythene, and Rahul Δ loethylene powder are added to prevent heat shrinkage of the C-cured resin. Avoid lowering the
It can improve thermal conductivity. Furthermore, in order to change the physical properties of the cured resin as necessary, in addition to the resin (a) whose main components are bismaleimide and 1 to riazine resin monone and the epoxy resin (b), other resins,
For example, modification can be achieved by blending a small amount of polyester resin, polyimide resin, polyesterimide resin, etc. The mixing ratio of resin and solvent (resin concentration) can be changed arbitrarily depending on the coating method, and if necessary, the resin can be raised to a high degree and heated during painting to lower the viscosity. It may also be covered with a thorn.

The solvent-based varnish obtained in this way contains imide bonds and has excellent heat resistance, moisture resistance, electrical insulation, and mechanical properties, and is used in the Electrical and Electronics Industry, which requires these properties.
5 and is suitable as a semiconductor-related varnish. In addition, it has good processability and does not attack the emulsion on the screen, and has no toxicity or odor. Applications include coil impregnating varnish for electrical insulation, resin insulation layer forming varnish for various hybrid ICs, and varnish for alignment protective film of liquid crystal cells.
It can be used as a moisture-resistant protective film varnish for semiconductor chips such as ICs, LSIs, and diodes.

[Embodiments of the invention] Next, the present invention will be specifically explained with reference to Examples.

Hereinafter, "parts" means "parts by weight."

Example 1 80 copies of L vinyl]-1-828 and BT2170 (
A viscous brown varnish (A>It's 1U.

Example 2 - 100 parts of [P]-1 to 1007 were dissolved at 90 parts in 180 parts of dienasine glycol monobutyl ether alethate.
After melting at °C, 20 parts of B T 2170 was added and uniformly dissolved to obtain a viscous varnish (B).

Example 3 200 parts of ECNI 280 (manufactured by Ziba Geigy) were added to diethylene glycol monobutyl ether arede-1.
After dissolving in ~600 parts of solvent at 80°C, 200 parts of 8-2170 were added and mixed at 100°C to obtain a viscous and transparent varnish (C).

Comparative Example 1 39 parts of hexahydrophthalic anhydride and 1 part of triethylamine were added to 61 parts of Epicoat 828 to obtain a common epoxy resin solution (D).

Comparative Example 2 A polyimide resin solution (E) having a resin content of 17% was obtained by reacting equivalent amounts of 4.4'-diaminodiphenyl needle and pyromellitic dianhydride in N,M-dimethylacetamide.

The varnish obtained in each of the above examples and comparative examples was
-C-2103 was subjected to a quasi-site test a, and the test results and the test results with various substrates are shown in Table 1. The curing conditions were 180'CX 1 hour. Furthermore, using the varnishes obtained in the Examples and Comparative Examples, approximately 70 m of annealed copper wire of <1 mmφ was attached to a round bar of fimmφ as shown in FIG.
A helical coil 1 made by winding it to a width of m is processed and placed on a load cell 2 with a width of s o m m.The adhesive strength is such that the load reaches each temperature at a load speed of 50 m/min from the direction of the arrow U. (bending strength) and the results are shown in Table 1 lc0 [Effects of the Invention] As is clear from the above 31 results, the solvent-based varnish of the present invention has good processability and workability, has good insulation properties, Because it has heat resistance, it has excellent humidity resistance and electric current fj1 at high temperatures.
Moreover, it does not attack the screen emulsion, has no toxicity or odor, and has good adhesion to various substrates.
J5 also has excellent adhesive strength and temperature characteristics, which epoxy resins and polyimide resins alone do not have.

[Brief explanation of drawings]

FIG. 1 is a sketch showing a method for measuring the adhesive strength of varnish. 1... Helical coil, 2... Loadrel. Figure 1

Claims (1)

[Scope of Claims] 1. A resin composition consisting of (a) a resin containing hismaleimide and triazine resin monomer as main components and (1) an epoxy resin is mixed with dielene glycol monoalkyl ether 7cetate or diethylene glycol monoalkyl ether A solvent-based varnish characterized by being dissolved in an ethylene glycol dialkyl ether solvent. 2. The blending ratio of (a) a resin whose main components are bismaleimide and triazine resin monomer and (b) an epoxy resin is in the range of 10:90 to 90:10 (heavy ratio). A solvent-based varnish according to claim 1. 3 (a) Hismaleimide and 1 heliazine resin tops
The resin whose main components are hismaleimide represented by the general formula, dicyanate represented by the general formula N=C-0-△r2-0-C=N, and a ring containing 3 or more molecules of dicyanate in the molecule. 1 heliazine resin having chemically polymerized 1 to lyazine rings and having a cyanide 1-group (N=C-0-) at the molecular end, △
3. The solvent-based varnish according to claim 1 or 2, wherein r + and A r 2 represent a divalent aromatic group of - or mino.