JPH0684473B2 - Moisture and heat resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a novel heat-resistant resin composition having excellent moisture resistance. More specifically, the present invention relates to a moisture-resistant heat-resistant resin composition containing a polyamide-imide resin and an epoxy resin as main components and useful as a material for electronic parts and the like.

[Prior Art] Conventionally, a polyimide resin has been known as a material having excellent heat resistance, but it has a problem in terms of moisture resistance, and improvement in processability has been desired.

Also, in the polyamide-imide resin proposed to improve these problems (see, for example, Japanese Patent Publication No. 49-35076), the heat resistance which has recently become particularly severe, for example, 300 ° C. 10
It did not pass the solder heat resistance test of seconds, and needed improvement in terms of dimensional stability during heat and humidity.

On the other hand, the epoxy resin that has been widely used in the past has good moldability,
Although it is excellent in terms of adhesiveness, it is well known that it is inferior in heat resistance to polyimide resin or polyamide-imide resin, etc., and that it also has problems in flexibility and softness. A resin material that meets the required standard has not been realized. Under these circumstances, proposals have been made to use both of them, that is, the polyamideimide resin and the epoxy resin in combination. Proposal of a heat-meltable resin composition composed of an aromatic polyamideimide resin having a bond at the 1,3 position of an aromatic nucleus and an epoxy resin (JP-A-55-48242) and composed of a polyamideimide resin and an epoxy resin Adhesive composition (JP-A-51-73034
This is the proposal etc.

However, these proposals are insufficiently examined in terms of moisture resistance at high temperatures, probably because of the difference in their purposes, and both have a problem in dimensional stability during heat and humidity, and high demands in the field of electronic parts etc. It has a problem that it is difficult to adopt as a material satisfying the characteristics.

[Problems to be Solved by the Invention] The present inventor has passed the present situation, that is, passed the recently required severe heat resistance test, and also has excellent moisture resistance, and thus has excellent dimensional stability during heat and moisture resistance. In view of the current situation that has not been realized, as a result of earnest research to provide a resin material satisfying these requirements, a resin material satisfying the above requirements by blending a specific amount of an epoxy resin with a specific polyamide-imide resin Heading The present invention has been completed. That is, the present invention relates to 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 resin having an epoxy equivalent of 50 to 1000 having at least two epoxy groups in the molecule. A moisture-resistant heat-resistant resin composition, which comprises an organic solvent and / or a curing agent if necessary in an amount of up to 300 parts by weight.

[Where Ar is (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 of 2 or more. ] Is provided.

The present invention will be described in detail below.

The organic polar solvent-soluble aromatic polyamideimide resin used in the present invention has the general formula Where Ar is (However, R is a hydrogen atom, a halogen atom, or an alkyl group,
X represents a divalent residue represented by an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group or a methylene group), preferably X is an oxygen atom, a sulfur atom or a sulfonyl group, and particularly preferably X is an oxygen atom, for example, an aromatic polyamide-imide resin containing 4,4'-diaminodiphenyl ether as an aromatic diamine component.

A reduced viscosity of 0.8 to 3.5, preferably 1.0 to 3.0 is used. If the reduced viscosity is too low, there is a problem in heat resistance and flexibility, and cracks tend to occur after film formation. On the other hand, if the reduced viscosity is too high, the compatibility with the epoxy is lowered, causing problems such as separation during curing.

The aromatic polyamideimide resin used in the present invention is a known method, for example, an aromatic diamine and trimellitic anhydride chloride are reacted in an organic polar solvent, or an aromatic diisocyanate and trimellitic anhydride are reacted in an organic polar solvent. It can be produced by reacting with.

As the aromatic diamine used in the present invention, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4 '
-Diaminobenzophenone, 4,4'-diaminodiphenylmethane can be mentioned. Of these, 4,4'-diaminodiphenyl ether is particularly preferable from the viewpoint of moisture resistance.

The epoxy resin used in the present invention has at least two epoxy groups per molecule, and can be obtained, for example, by reacting bisphenol A with epichlorohydrin.

Epoxy resin represented by (n has an average value of 0 to several 10), or a reaction product of novolak resin and epichlorohydrin A novolac epoxy resin represented by (m has an average value of 0 to about 5) is preferred. From the viewpoint of moisture resistance, bisphenol A type epoxy resin is particularly preferable, and halogenated bisphenol A type epoxy resin is most preferable. The epoxy equivalent of the above epoxy resin is preferably from 50 to 1000, and particularly preferably from 150 to 500. It should be noted that if the epoxy equivalent is too large, the compatibility with the polyamide-imide resin deteriorates and the flexibility and moisture resistance also decrease. Aromatic polyamide-imide resin 100
It is selected from the range of 25 to 300 parts by weight with respect to parts by weight. It is preferably 50 to 200 parts by weight. If it is less than 25 parts by weight, the moisture resistance and adhesiveness will be clearly reduced, and if it exceeds 300 parts by weight, the heat resistance and flexibility will be deteriorated.

The composition of the present invention may be cured by itself, but a curing agent for epoxy resin may be added in an amount of 1 to 500 parts by weight per 100 parts by weight of the polyamide-imide resin in order to improve curing time and mechanical properties. As the curing agent, diaminodiphenyl ether, diaminodiphenyl sulfone, phenylenediamine, trimellitic anhydride and the like are preferable 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-2pyrrolidone, hexamethylphosphoramide, halogenated cresol or a mixed solvent thereof, or the like. And other conventional solvents.

As the compounding method of the composition of the present invention, any conventionally known compounding method can be used, but in particular, an aromatic polyamideimide resin is added to the polar organic solvent described above, and a stirrer, a ball mill,
A method of sufficiently dissolving with a three-roll mill or the like, then adding an epoxy resin and uniformly mixing is preferable. The amount of the solvent used is usually selected from the range of 230 to 9900 parts by weight based on 100 parts by weight of the aromatic polyamideimide resin.

The resin composition of the present invention thus obtained is usually used after being dissolved in a solvent and applied to an object and then heat-treated at 90 to 200 ° C, preferably 130 to 180 ° C to form a coating film. . It can also be used for printing. In addition, when a molded product is formed by casting or the like, the solvent may be evaporated by an appropriate means and, if necessary, a heat treatment may be used.

Various additives can be added to the composition of the present invention. For example, glass fiber, glass powder, heat-resistant fiber or the like can be added as an additive or reinforcing filler for imparting electrical characteristics such as conductivity, dielectric property and insulation property.

〔The invention's effect〕

The resin composition of the present invention has excellent heat resistance and humidity resistance, is also flexible, has excellent dimensional stability during so-called heat and humidity, and has good adhesiveness. Further, it is excellent in so-called low-temperature processability that it can be heat-cured at 200 ° C or lower.

Taking advantage of such excellent properties, the composition of the present invention can be used for materials in the field of electronic components such as flexible substrate materials, flexible laminated materials, encapsulants, overcoat materials, and undercoat materials, It is used as a film, sheet, paint, adhesive, etc.

〔Example〕

The present invention will be described below with reference to examples and comparative examples. The measured values shown in the following examples and comparative examples are measured by the following measuring methods.

Moisture permeability (moisture resistance) It was performed according to JIS Z0208.

A 100 μm thick test piece was measured by the cup method under the conditions of 40 ° C. and 90% RH.

Glass transition point (Tg) 5 mm by the tensile load method using a thermomechanical analyzer manufactured by Rigaku Denki Co., Ltd.
The test piece of × 20 mm was measured at a heating rate of 5 ° C./min.

Folding resistance was performed according to JIS P8115. (MIT type tester) The thickness of the test piece was 100μ.

Tensile strength Using Tensilon tensile tester manufactured by Toyo Baldwin,
It was measured with a test piece having a width of 6 mm and a thickness of 100 mm.

Example 1 100 parts by weight of an aromatic polyamideimide having a reduced viscosity of 1.4 obtained from 4,4 ′ diaminodiphenyl ether and trimellitic anhydride chloride and an epoxy resin AER745 manufactured by Asahi Kasei Corporation
(Brominated bisphenol type epoxy resin, epoxy equivalent
415) 40 parts by weight were dissolved in 400 parts by weight of N-methyl-2-pyrrolidone.

The obtained composition is coated on a flat plate and then at 130 ° C for 1 hour, then 1
It was cured at 80 ° C. for 1 hour to obtain a film. When the moisture resistance of the film was measured, it showed an excellent moisture resistance of 5.0 g / m ² .24 Hr.100μ. The glass transition point (Tg) of this product is 20.
It was found to have excellent heat resistance at 3 ° C.
When bending resistance and tensile strength were measured as mechanical properties
It was 153 times / 100μ and 12.1 kg / mm ² .

When the above composition was applied onto a copper foil and then subjected to the same curing treatment, it was dipped in a solder bath at 300 ° C for 10 seconds, and then warped,
There was no change in shape such as peeling or foaming. Furthermore, this is 40 ℃
The same test was carried out after storage under 90% RH for 24 hours, but there was no abnormality and excellent heat and humidity resistance was exhibited.

Examples 2 to 5 (Table 1) Table 1 was prepared based on 100 parts by weight of an aromatic polyamideimide resin having various reduced viscosities obtained from 4,4'-diaminodiphenyl ether (DADPE) and trimellitic acid chloride.
An epoxy resin was blended according to the formulation shown in 1 above, and various curing agents were added thereto and dissolved in an organic solvent to produce a composition.

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

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 as in Example 4,4'-diaminodiphenyl ether ( Resin obtained from DADPE) and trimellitic acid chloride was used. The results are shown in Table 1, which has a low humidity resistance and has a problem in use during heat and humidity.

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 a film could not be formed.

In Comparative Example 3, it can be seen that the kind of the aromatic polyamide-imide resin is outside the present invention and is inferior in terms of moisture resistance and bending resistance.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication location C08L 79:08) (72) Inventor Yuichiro Mori 648 Hirookaue, Haruno-cho, Agawa-gun, Kochi Prefecture NITPON KOSHI KOGYO KOGYO CO., LTD. In-house (56) Reference JP 60-49635 (JP, A) JP 55-106260 (JP, A) JP 58-79020 (JP, A)

Claims (3)

[Claims] 1. An epoxy resin having an epoxy equivalent of 50 to 1000 having 100 parts by weight of an organic polar solvent-soluble aromatic polyamideimide resin represented by the following general formula and having a reduced viscosity of 0.8 to 3.5 and having at least two or more epoxy groups in the molecule. A moisture-resistant heat-resistant resin composition comprising 25 to 300 parts by weight of an organic solvent and / or a curing agent if necessary. Where Ar is (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 of 2 or more. 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 9900 parts by weight.