JPH0629366B2 - Resin composition - Google Patents

Description

The present invention relates to a reactive injection molding resin for casting, which is excellent in impact resistance, heat distortion temperature, and workability for structural materials and mechanical component materials. It relates to a composition.

Structure of Conventional Example and Its Problems Conventionally, in general, a reactive injection molding (hereinafter referred to as RIM) resin composition for structural materials and mechanical parts materials is made from urethane resin or epoxy resin as a starting material. there were.
However, although casting materials and RIM materials obtained using urethane resin as a starting material are excellent in impact resistance, they generally have a heat distortion temperature (18.6 Kg load) of 70 to 8
The disadvantage was that it was low at 0 ° C. Next, RIM and casting materials using epoxy resin as a starting material are excellent in heat distortion temperature, but generally have a low impact value and have a drawback that a molding cycle is required for 3 to 4 hours. on the other hand,
On the other hand, in JP-A-57-94019, about 1 mol of a bis (2-oxazoline) compound contains about 1.
A polyester polyamide characterized by reacting at a ratio of 7 equivalents or less has been proposed. This is a castable resin composition having excellent heat distortion temperature (80 ° C to 100 ° C) and impact resistance (Izod, notched, 6 to 7 [Kg-cm / cm]). However, this composition is certainly superior to casting resins such as conventional epoxy resins and urethane resins, namely heat resistance (excellent characteristics of epoxy resin) and impact resistance (excellent characteristics of urethane resin). )
Although they have both, the heat deformation temperature of 100 ° C or more and the impact strength of 1 required for the current exterior materials and parts materials.
The physical property values of 0 [Kg-cm / cm] (with Izod and notch) or more were not satisfied.

OBJECT OF THE INVENTION The object of the present invention is to solve the above-mentioned problems and to combine the advantages of epoxy and urethane resins, which have been used as conventional casting materials having excellent heat resistance and impact resistance. Another object of the present invention is to provide a resin composition useful as a material for casting or RIM (reactive injection molding).

Composition of the Invention The resin composition of the present invention comprises 2,2 ′-(1,3-phenylene) -bis (2-oxazoline), 2,2 ′-(1,4).
-Phenylene) -bis (2-oxazoline) at least one bis (2-oxazoline) compound, at least one aromatic polycarboxylic acid selected from terephthalic acid and isophthalic acid, and adipic acid, azelaic acid, sebacine Acid, α, ω-polybutadiene carboxylic acid, butane-1,2,3,4-tetracarboxylic acid, at least one kind of polycarboxylic acid, salicylic acid, and triphenyl phosphite Value is 10
[Kg-cm / cm] (with Izod and notch) or more, heat distortion temperature of 100 ° C. (18.6 Kg load) or more, viscosity of liquid mixture before gelling and reaction is 500 centipoise or less, It is a completely new and excellent material with a molding cycle of less than 1 hour, which is not found in conventional resin compositions. This resin composition is a combination of a bis (2-oxazoline) compound, an aromatic polycarboxylic acid and a flexible polycarboxylic acid, and salicylic acid. , A resin composition having excellent workability of RIM, high impact value, and high heat distortion temperature. In the present invention, the bis (2-oxazoline) compound acts as a main agent, and has 2 Any number of oxazoline rings may be bonded, for example, 2,2 '-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,4-phenylene) -bis (2 -Oxazoline), 2,2 '-(1,2-phenylene) -bis (2-oxazoline), 2,2'-(1,2
-Phenylene) -bis (4-methyl-2-oxazoline), 2,2 '-(1,3-phenylene) -bis (4-
Methyl-2-oxazoline), 2,2 '-(1,4-phenylene) -bis (4-methyloxazoline), 2
2 '-(1,2-phenylene) -bis (5-methyl-2)
-Oxazoline), 2,2 '-(1,3-phenylene)
-Bis (5-methyl-2-oxazoline), 2,2'-
It may be (1,4-phenylene) -bis (5-methyl-2-oxazoline). The aromatic polycarboxylic acid functions to raise the heat distortion temperature and may be terephthalic acid or isophthalic acid. The flexible polycarboxylic acid acts to increase the impact resistance value, and adipic acid, azelaic acid,
It may be sebacic acid, α, ω-polybutadiene dicarboxylic acid, butane-1,2,3,4-tetracarboxylic acid. Triphenyl phosphite, which is a catalyst, acts to open and crosslink the oxazoline ring. Salicylic acid, which is an additive, serves to lower the viscosity of the liquid mixture before the reaction and gelation, and to improve the workability when defoaming.

Description of Embodiments Next, the present invention will be described in more detail with reference to embodiments.

Example 1 2,2 ′-(1,3-phenylene) bis (2-oxazoline), terephthalic acid, adipic acid, azelaic acid, sebacic acid, α, ω-polybutadiene dicarboxylic acid, butane-1, 2,3,4-tetracarboxylic acid, each of which is placed in a beaker and left in a constant temperature bath at 200 ° C for about 1 hour,
Melt in liquid form. Liquefied 2,2 '-(1,3-
138 g of phenylene) -bis (2-oxazoline),
20 g of terephthalic acid, 20 g of α, ω-polybutadiene dicarboxylic acid and 20 g of salicylic acid are added and mixed. Furthermore, to this liquid mixture, liquid adipic acid 22
1.0 g by weight of the catalyst was mixed and sufficiently stirred. That is, 2,2 '-(1,3-phenylene)-
69 wt% bis (2-oxazoline) and 1 terephthalic acid
0 wt%, adipic acid 10 wt%, salicylic acid 10 wt%
And 1 wt% of the catalyst will be agitated. After vacuum degassing with this, it was poured into a mold for a heat deformation test piece and a mold for an impact test piece, and allowed to stand in a constant temperature bath at 200 ° C. for about 30 minutes, and then left at room temperature for 30 minutes and air-cooled. Then, the mold was removed to obtain a test piece. (This test piece is referred to as No. 1 for convenience)
Similarly, liquefied 2,2 '-(1,3-phenylene) -bis (2-oxazoline), terephthalic acid, α,
Three mixtures of ω-polybutadiene dicarboxylic acid were prepared, and azelaic acid, sebacic acid, 1, 2,
20 g each of 3,4-tetracarboxylic acid was added, and 1.0
A wt% catalyst was added, and a heat distortion temperature test piece and an impact resistance test piece were obtained in the same manner as described above. (For convenience, these test pieces are No. 2, No. 3, No. .4). The heat deformation temperature and the impact strength of these were measured by a predetermined test method. The results are shown in Table 1.

It can be seen that the impact value is 10 [Kg-cm / cm] and the heat distortion temperature is 100 ° C or higher.

[Example 2] 2,2 '-(1,3-phenylene) -bis (2-oxazoline) obtained in (Example 1) was replaced with 2,2'-(1,4-phenylene) -bis (2-oxazoline). ), Terephthalic acid was changed to isophthalic acid, and the impact value and heat distortion temperature were measured in the same manner as in (Example 1). The result is
It is shown in Table 2.

It can be seen from Table 2 that the impact value is 10 [Kg-cm / cm] or more and the heat distortion temperature is 100 ° C or more.

As described above, according to the resin composition of the present invention, the heat distortion temperature can be improved by adding the aromatic polycarboxylic acid, and the impact resistance can be improved by adding the flexible polycarboxylic acid. The heat distortion temperature is 100 ℃ or more, and the impact value is 10 [Kg-cm by the combination of these compounding amounts.
/ Cm] (with Izod, notch) or more, about 5 times or more the impact strength of the epoxy resin, which is a conventional casting material,
This is effective in obtaining a physical property value which is 1.5 times or more the heat distortion temperature of the urethane resin. Further, by adding salicylic acid to the combination of these materials, it is possible to obtain a completely new physical property with excellent workability such that the viscosity before reaction and gelation is 500 centipoise or less. Is.

Claims (1)

[Claims] 1. At least one of 2,2 '-(1,3-phenylene) -bis (2-oxazoline) and 2,2'-(1,4-phenylene) -bis (2-oxazoline). 69 wt% of bis (2-oxazoline) compound, 10 wt% of at least one aromatic polycarboxylic acid of terephthalic acid and isophthalic acid, adipic acid, azelaic acid, sebacic acid, α, ω-polybutadienecarboxylic acid, butane- A resin composition comprising 10 wt% of at least one polycarboxylic acid of 1,2,3,4-tetracarboxylic acid, 10 wt% of salicylic acid, and 1 wt% of triphenylphosphite.