JPS62151458A - Moisture-and heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled flexible composition outstanding in both heat and moisture resistances, with high dimensional stability and adhesivity when exposed to heat and/or moisture, suitable as raw material for electronic parts, etc., by incorporating specific polyamide-imide resin with specified amount of an epoxy resin. CONSTITUTION:The objective composition can b obtained by incorporating (A) 100ps.wt. of an organic polar solvent-soluble aromatic polyamide-imide resin with a reduced viscosity 0.8-3.5 of formula I [Ar is divalent residue of formula II (R is H, halogen, etc.; X is oxygen atom, etc.); in is >=2] with (B) 25-300(pref. 50-200)pts.wt. of an epoxy resin with an epoxy equivalent 50-1,000 having in the molecule at least two epoxy groups [e.g. of formula III (n is 0-10), etc.] and, if needed, (C) 230-9,000ps.wt. of an organic solvent (e.g. N,N-dimethylformamide) and/or (D) 1-500pts.wt. of a curing agent (e.g., diaminodiphenyl ether).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel heat-resistant resin composition with excellent moisture resistance. More specifically, the present invention relates to a moisture-resistant and heat-resistant resin composition that is useful as a material for electronic parts and the like, and whose main components are a polyamide-imide resin and an epoxy resin.

[Prior Art] Polyimide has conventionally been known as a material with excellent heat resistance, but it has problems in terms of moisture resistance, and improvements have been desired in terms of processability and the like.

In addition, polyamide-imide resins that have been proposed to improve these problems (for example, see Japanese Patent Publication No. 49-35076) do not pass the soldering heat resistance test, which has recently become particularly strict, such as 300' CIO seconds. In addition, improvements were needed in terms of dimensional stability under heat and humidity.

On the other hand, epoxy resin, which has been widely used in the past, has poor moldability.
Although it has excellent adhesive properties, it is well known that it is inferior to polyimide resin or polyamide-imide resin in terms of heat resistance, and it also has problems in terms of flexibility and softness. Resin material that meets the required standards]'
It didn't happen in the old days. Under these circumstances, proposals have already been made to use a combination of both, ie, a polyamideimide resin and an epoxy resin.

Proposal of a heat-meltable resin composition consisting of an aromatic polyamide-imide resin having bonds at the 1 and 3 positions of the aromatic nucleus and an epoxy resin (Japanese Unexamined Patent Publication No. 1982-48242) and a composition consisting of a polyamide-imide resin and an epoxy resin This is a proposal regarding a care composition (Japanese Patent Application Laid-open No. 73034/1983).

However, perhaps due to the difference in purpose of these proposals, insufficient consideration has been given to moisture resistance under high temperatures, and all of them have problems with dimensional stability under heat and humidity, and meet the high demands of the electronic component field. The problem is that it is difficult to use as a material that satisfies the characteristics.

“Problem to be Solved by the Invention 1 The present inventor has proposed that such a ring, that is, +X
Considering the current situation where there is no resin material that has passed the heat resistance test, has excellent moisture resistance, and therefore has excellent dimensional stability under heat and humidity conditions, we provide resin materials that meet these requirements. As a result of intensive research, the present invention was completed by discovering a resin material that satisfies the above requirements by blending a specific amount of epoxy resin with a specific polyamide-imide resin. Indicated reduced viscosity 0.8
~3.5 organic polar solvent soluble aromatic polyamideimide resin 1()0 small part and 25 to 300 parts by weight of epoxy resin having at least two or more epoxy groups in the molecule and 150 to 1000 epoxy resin as necessary 2
n represents an integer of 2 or more. ].

The present invention will be explained in detail below.

The organic polar solvent-soluble aromatic polyamideimide resin used in the present invention is ((F-) LR is a hydrogen atom, a halogen atom, or an alkyl group, and X is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a methylene It is preferable that X is an oxygen atom, a sulfur atom, or a sulfonyl group, and it is particularly preferable that X is an oxygen atom, such as 4,4°-diaminodiphenyl ether. ″
rj Aromatic polyamide-imide resin as an aromatic diamine component.

Reduced viscosity is 0.8-3.5, preferably 1.0-3.0
Noraoka is used. )! If the original viscosity is too low, the heat resistance
There is a problem with flexibility, and cracks tend to occur after film formation.

Furthermore, if the reduced viscosity is too high, the compatibility with epoxy will decrease, causing problems such as separation during curing.

The aromatic polyamide-imide resin used in the present invention can be prepared by a known method, for example, by reacting an aromatic diamine and trimellitic anhydride chloride in an organic polar solvent, or by reacting an aromatic diisocyanate and trimellitic anhydride with an organic (
It can be produced by reacting in an aqueous solvent.

Aromatic diamines used in the present invention include 4,4°-diaminodiphenyl ether, 4,4'-diaminosifenyl sulfide, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, and 4,4'-diamino Mention may be made of diphenylmethane.

Among these, 4,4'-diaminodiphenyl ether is particularly preferred from the viewpoint of moisture resistance.

The epoxy resin used in the present invention has at least 2 g of epoxy groups per molecule and is obtained, for example, by the reaction of hisphenol A and shrimp chlorohydrino.

Preferred examples include epoxy resins represented by (n is O-, so the average value is 10), or novolac epoxy resins represented by a reaction product of a novolak resin and epichloromethane. Particularly preferred are bisphenol A type epoxy resins from the viewpoint of moisture resistance, and among these, halogenated bisphenol A type epoxy resins are most preferred.
The epoxy equivalent of the above-mentioned epoxy resin is preferably from 50 to 1,000, particularly preferably from 150 to 500. If the epoxy equivalent is too high, the compatibility with the polyamideimide resin may deteriorate (care must be taken as the intrinsic properties and moisture resistance will also decrease). The amount of the epoxy resin to be blended is selected from the range of 25 to 300 m most per 100 parts by weight of the aromatic polyamideimide resin. Preferably it is 50 to 200 parts by weight.

If it is less than 25 parts by weight, moisture resistance and adhesiveness will clearly decrease.
If it exceeds 0 parts by weight, heat resistance and flexibility will deteriorate.

The composition of the present invention can be cured by itself, but in order to improve the curing time and mechanical properties, a curing agent for epoxy resin may be added in an amount of 1 to 500 parts per 100 parts by weight of the polyamide-imide resin.
Parts by weight can be added.

As the curing agent, diaminodiphenyl ether, diaminodienoenyl sulfone, phenylene diamine, trimellitic anhydride, etc. are preferred from the viewpoint of heat resistance and moisture resistance.

The organic solvent used in the present invention is N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, hexamethylphosporamide, halogenated cresol, or a mixed solvent thereof, or a mixture thereof. and other commercially available solvents.

As for the compounding method of the composition of the present invention, any conventionally known compounding method can be used, but in particular, aromatic polyamideimide resin is added to the above polar organic solvent, using a counterfeiter, a ball mill, etc.
A preferred method is to thoroughly dissolve the mixture using a three-roll mill or the like, then add the epoxy resin and mix uniformly. The amount of solvent used is usually selected from the range of 230 to 9900 parts by weight per 100 parts by weight of the aromatic polyamideimide resin.

The resin composition of the present invention obtained in this manner has a temperature of 90 to 20% after being dissolved in a solvent and applied to an object.
Heat treatment is performed at 0°C, preferably 130 to 180'C, to form a coating film before use. It can also be used for printing. In addition, when the molded product is formed by casting or the like, the solvent may be evaporated by an appropriate means, and if necessary, the product may be heat-treated before use.

Various other additives may be added to the composition of the present invention. For example, glass fibers, glass powder, heat-resistant fibers, etc. can be added as additives or reinforcing fillers to impart electrical properties such as conductivity, dielectricity, and insulation.

〔Effect of the invention〕

The resin composition of the present invention has excellent heat resistance, moisture resistance, and flexibility, and also has excellent dimensional stability under heat and humidity conditions, and good adhesiveness. Furthermore, it has excellent low-temperature processability, meaning that it can be heat-cured at temperatures below 200°C.

Taking advantage of these excellent properties, the composition of the present invention can be used for materials in the field of electronic components, such as flexible substrates + former 1M, flexible laminated materials, sealing materials, overcoat materials, and undercoat materials. Other uses include films, sheets, paints, and adhesives.

〔Example〕

The present invention will be explained below with reference to Examples and Comparative Examples.

Incidentally, the measured values shown in the following Examples and Comparative Examples were measured by the following measuring method.

■Moisture permeability (moisture resistance) It was carried out according to JISZO208.

A test piece having a thickness of 100μ was measured using the cup method under the conditions of 40'C and 190%RH.

■Glass transition point (Tq) 5m by tensile load method using a thermomechanical analyzer manufactured by Rigaku Denki Co., Ltd.
Measurement was carried out using a test piece of m x 20 mm at a heating rate of 5° C./min.

■Bending strength Tested according to JIS P8115. (MIT type tester) The thickness of the test piece was 100μ.

■Tensile strength Using a Denjiron tensile tester manufactured by Toyo Baldwin,
The measurement was performed using a test piece with a width of 6# and a thickness of 100#.

Example 1 100ffi of aromatic polyamideimide with a reduced viscosity of 1.4 obtained from 4.4' diaminodiphenyl ether and trimellitic anhydride chloride! and 40 parts of epoxy resin AER745 (brominated bisphenol type epoxy resin, epoxy resin AER745 manufactured by Asahi Kasei Corporation) were added with N-methyl-2.
-Dissolved in 400 parts by weight of pyrrolidone.

The obtained composition was coated on a flat plate and cured at 130°C for 1 hour and then at 180°C for 1 hour to obtain a film.

The moisture resistance of the film-like material was measured to be 5.0'j/m.
, 24tlr, and 100μ.

Further, the glass transition point (Tq) of this material was 203°C, indicating that it had excellent heat resistance.

As for mechanical properties, the bending strength and tensile strength were measured and were 153 times/100μ, 12. It was 1Kg/mrrt.

When the above composition was applied onto a copper foil and subjected to a similar curing treatment and immersed in a 300° C. solder bath for 10 seconds, there was no change in shape such as warping, peeling, or foaming. After storing this at 40° C. and 90% RH for 24 hours, the same test was performed, but no abnormality was found, and it showed excellent heat and humidity resistance. , Examples 2-5 (Table 1) 4.4'-diaminodiphenyl ether (DADPE)
To 100 parts by weight of aromatic polyamideimide resins having various reduced viscosities obtained from and trimellitic acid chloride, an epoxy resin was blended in the proportion shown in Table 1, various curing agents were added thereto, and the mixture was dissolved in an organic solvent. , produced a composition.

Table 1 shows the moisture resistance, glass transition point, and mechanical properties (bending strength, tensile strength) of these.

Comparative Examples 1 to 3 (Table 1) As shown in Table 1, Comparative Example 1 is an example in which no epoxy resin was blended, and the aromatic polyamideimide resin was the same 4,4'-diaminodiphenyl ether (DADP) as in the example.
A resin prepared from E) and trimellitic acid chloride was used. As shown in Table 1, the results show that the moisture resistance is low and there is a problem in using it in hot and humid conditions.

Comparative Example 2 is an example in which an aromatic polyamideimide resin having a reduced viscosity outside the range of the present invention was used, and no film could be formed.

It can be seen that in Comparative Example 3, the type of aromatic polyamide-imide resin was outside the scope of the present invention, and the moisture resistance and bending resistance were inferior.

Claims (1)

[Scope of Claims] 1. 100 parts by weight of an organic polar solvent-soluble aromatic polyamideimide resin having a reduced viscosity of 0.8 to 3.5 represented by the following general formula and an epoxy equivalent having at least two or more epoxy groups in the molecule. 50~1000 epoxy resin 25~
A moisture-resistant and heat-resistant resin composition comprising 300 parts by weight of an organic solvent and/or a curing agent, if necessary. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Ar is ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R is a hydrogen atom, a halogen atom, or an alkyl group,
X represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a methylene group),
represents an integer greater than or equal to 2. 2. The resin composition according to claim 1, wherein the curing agent is present in an amount of 1 to 500 parts by weight. 3. The resin composition according to claim 1, wherein the organic solvent is present in an amount of 230 to 9,900 parts by weight.