JPS63280738A - Reaction molding resin composition and method for molding thereof - Google Patents

Abstract

PURPOSE:To obtain the titled composition having low water-absorption and excellent impact resistance and heat resistance, by mixing oxazoline with a guanamine containing spiroacetal ring or a heterocyclic amine and adding an alkyl halide to the mixture as a catalyst. CONSTITUTION:(A) Oxazoline is mixed with (B) a guanamine containing spiroacetal ring or a heterocyclic amine at a molar ratio (B/A) of 1-2 and the obtained mixture is compounded with (C) 0.1-10wt.% of an alkyl halide as a catalyst to obtain the objective composition. The molding of the composition is carried out by separately heating a liquid composed of the component A and a liquid produced by mixing the components B and C, injecting and mixing the liquids in a mixing head and injecting the mixed liquid into a mold placed in a vacuum chamber.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a reaction molding resin composition used for the production of a wide variety of resin molded products in small quantities, and a molding method using the same.

Conventional technology Conventionally, urethane R was mainly used for the production of a wide variety of resin molded products in small quantities.
IM materials, epoxy RIM materials, etc. have been used, but these materials: ■ Urethane RIM materials have a low heat resistance of 70°C to 80'C;
The impact properties of these materials were poor (less than 10 to 9-tfi/(m) for isot and notched materials. For this reason, nylon RIM material was considered as an alternative material to these materials.This nylon material is the flexural modulus (20000
[K, 4-] or higher), impact properties (with an isot notch, 1 ()K, 9-cm or higher) and heat distortion temperature (1a, cs KSI load.

(120℃ or higher), and it is liquid and has low viscosity, so the mold for molding does not need to be made of metal.
It has been used to create prototypes, which is one of the ways to produce a wide variety of products in small quantities. As this nylon RIM molding for prototypes is put into practical use, technologies that can handle small-lot, wide-variety production using nylon RIM materials and the like are being studied.

Problems to be Solved by the Invention However, in conventional nylon RIM materials, the polyamide group, which is a constituent component of the nylon RIM material, has the property of absorbing moisture, resulting in decreases in physical properties, changes in dimensions, etc. was seen.

The current water absorption rate is 20 wt% (atmospheric equilibrium), and the dimensional change rate is 0.18%. For this reason, it is difficult to use the nylon RIM material as an actual product, and the development of commercialization is currently delayed.

In view of the above problems, the present invention provides a reaction molding resin composition that has low water absorption and excellent impact resistance and illumination heat resistance, and a molding method using the same.

Means to solve the problem In order to solve the above problem, the first invention of the present invention is as follows:
Mexazoline and a gufnamine having a spiroacetal ring or a heterocyclic amine are mixed at a molar ratio of 1.0 to 2.0 with respect to oxazoline, and a halogenated alkyl is added as a catalyst to 0.0 to 2.0.・'wt% to 1
．． It is an object of the present invention to provide a reaction molding resin composition which is mixed with 0% by weight.

In addition, the present invention/η] The second invention is a compound in which oxazoline and guanamine having a spiroacetal ring or a heterocyclic amine are combined in a molar ratio of 1.0 to 2.0 with respect to oxazoline. Inside, 0.1% to 1.0% by weight of alkyl halide is mixed as a catalyst, and a filler with an average aspect ratio of 6 to 20 and a spherical or flaky shape with an average aspect ratio of 1 to 3 are mixed. Another object of the present invention is to provide a reaction molding resin composition containing 10% by weight or more and 60% by weight or less of a fibrous filler.

Further, in the third aspect of the present invention, oxazoline is used as liquid A, and the guanami/heterocyclic amine having a spiroacetal ring is contained in a molar ratio of 1.0 to 2.0 with respect to the oxazoline.
Liquid B, which is a mixture of 0.1% to 1.0% by weight of alkyl halide as a catalyst, is heated and injected into the mixing head and mixed. It is an object of the present invention to provide a method for molding a reaction molding resin composition, in which the resin composition is injected into a mold in a vacuum chamber to mold a molded article.

Function In the first invention of the present invention, the guanamine or heterocyclic amine having a spiroacetal ring lowers the water absorption rate of the composition by reacting and curing with the oxazoline, and also reduces the impact resistance from its molecular skeleton. This will improve the results.

Further, in the second invention of the present invention, the guanamine having an acetal ring or the heterocyclic amine of the first invention of the present invention is contained in a molar ratio of 1.0 to 2.0 with respect to the oxazoline. and to which 0.1% to 1.0% by weight of alkyl halide was added as a catalyst,
By mixing a filler with an average aspect ratio of 5 or more and 20 or less, the mechanical properties of the material will be strengthened.

Further, in the third aspect of the present invention, the mixing head mixes the oxazoline in the first aspect of the present invention and guanamine having a spiroacetal ring or a heterocyclic amine, and the vacuum chamber mixes the oxazoline according to the first aspect of the present invention with a guanamine having a spiroacetal ring or a heterocyclic amine. Let M be the action that removes.

EXAMPLE An example of the present invention will be described below. Oxazoline is used as liquid A, and guanamine consisting of a spiroacetal ring is
Molar ratio with oxazoline: o, 9°1.0, 1.3
, 1.5, 1.7, 2.0,
B1.propyl bromide was used as a catalyst and was adjusted to have a weight ratio of 0.1. B2. B3゜B4. B
5. It is called B6 liquid. Next, a mixture of liquid A and each of liquids B1 to B6 was poured into a mold (molding mold) at 150°C to prepare test pieces having six different molar ratios. These six types of test pieces were allowed to absorb moisture in a constant temperature and humidity environment of 23°C, 960RH, and the time taken to reach equilibrium was compared with that of a conventional RIM composition (Bo), and the results are shown in Table 1. It shows.

Table 1 From these results, guanamine has a molar ratio of 1.0 to 2.
．． It can be seen that in the case of up to 0 (B2 to B6), the time until the water absorption state reaches equilibrium is extended four times compared to the conventional case. Similar results were obtained using a heterocyclic amine. Regarding the catalyst, if it is 0.5% by weight or more,
The result was that the material burnt and yellowed, and it was found that the weight fraction of the catalyst was preferably 0.1% to 0.5% by weight.

Next, a second embodiment of the present invention will be described.

Oxazoline and heterocyclic amine (oiled shell epoxy) blended in the first embodiment of the present invention.

Epomate YOO2) is mixed at a molar ratio of 1.0, and propyl bromide is mixed at 0.1% by weight,
Furthermore, among them are milled fibers (Nitto Boseki ■, F 104) with an average aspect ratio of 11.

Glass peas with an average aspect ratio of 1 (
Toshiba Baro Sotini■, 30μ or less) is 10, 20
, 30, 40, and 455% by weight. For convenience, these are referred to as C1, C2, C3°C4, and C5. Pour these into a mold to prepare a test piece, and
The time required for the water absorption state to reach equilibrium was measured in the same manner as in Example 1. The results are shown in Table 2.

Table 2 From these results, it can be seen that the time it takes for the water absorption state to reach equilibrium is nearly four times longer than in the conventional case. Here, when a filler with an average aspect ratio of 20 or more is used, the viscosity increases significantly due to the large fiber length.
Not suitable for molding. Further, as a filler for a nylon RIM material, if the average aspect ratio is 5 or less, it does not function as a reinforcing agent, and no reinforcing effect can be obtained.

Next, a third embodiment of the present invention will be described with reference to the drawings.

Figure 1 shows the rubber mold 6 used to mold Master Model M.
It is. This was left to warm up in a constant temperature bath at 160° C. for 3 hours. On the other hand, oxazoline liquid A and heterocyclic amine (oiled shell epoxy ■).

Solution B, which is a mixture of Ebomate YOO2) and octyl bromide in an amount of 0.1 weight, was left in an oil bath at 130° C. for 1 hour to dissolve. These A liquid and B liquid are transferred to the tank 1 shown in FIG. The catalyst is poured into the tank 2 and the catalyst is poured into the tank 9, and at the same time, the tip of the static mixer 4 for mixing the three liquids is connected to the gate opening of the rubber mold 6 heated to 150'C. Next, these are placed in a vacuum chamber 7 and then degassed through a suction port 8. After confirming that the inside of the vacuum chamber is -76 cm HCJ, the mixing valve 3 is opened and the mixed liquid is poured into the rubber mold 6. After the influx,
The vacuum chamber is left to stand for about 6 minutes to return to normal pressure, and the gates and pads of the oxazoline compound, which is a replica of the master model molded in the rubber mold 6, are removed and finished.

This molded product was left at 23°C and 60RH for 200 hours,
A comparison was made with one made of conventional nylon RIM material. It is shown in Table 3.

Table 3 From these results, a material with a dimensional change rate of Z or less was obtained compared to the conventional nylon RIM material.

The molded product obtained by this method had fewer bubbles and had an excellent appearance compared to conventional molded products.

Effects of the Invention As described above, according to the first aspect of the present invention, the molar ratio of oxazoline and guanamine or heterocyclic amine having a spiroacetal ring to oxazoline is 1.0.
By mixing 0.1% to 1.0% by weight of alkyl halide as a catalyst into the mixture at a temperature within 2.0 and curing the composition, the water absorption rate of the composition decreases and the water absorption state The time it takes to reach equilibrium is several times longer than that of conventional methods, and its molecular framework improves impact resistance.

According to the second aspect of the present invention, the composition according to the first aspect of the present invention contains a filler having an average aspect ratio of 5 or more and 20 or less, and a spherical or flaky filler having an average aspect ratio of 1 or more and 3 or less. Alternatively, by mixing fibrous filler in an amount of 10% by weight or more and 60% by weight or less, the water absorption rate of the composition decreases as in the first aspect of the present invention, and the time required for the water absorption state to reach equilibrium is Moreover, the mechanical properties of the composition are improved by several times or more.

According to the third aspect of the present invention, the A solution made of oxazoline and the B solution made of a spiroacetal ring or a heterocyclic amine and an alkyl halide are respectively heated and then injected into the mixing head. The molded article is mixed by
The rate of dimensional change due to water absorption is less than a fraction of that of conventional products, and the product has an excellent appearance with fewer bubbles.

[Brief explanation of the drawing]

Figure 1 is a perspective view of the master model, Figure 2 is nylon R
FIG. 1 is a schematic diagram of an apparatus used for molding using an IM material composition. 4... Static mixer (mixing head), 6... Rubber mold (molding mold), A...
...Vacuum chamber.

Claims (3)

[Claims] (1) Oxazoline and guanamine or heterocyclic amine having a spiroacetal ring are mixed in a molar ratio of 1.0 to 2.0 with respect to oxazoline, and an alkyl halide is used as a catalyst, A reaction molding resin composition mixed with 0.1% to 1.0% by weight. (2) Oxazoline and guanamine or heterocyclic amine having a spiroacetal ring are mixed at a molar ratio of 1.0 to 2.0 with respect to oxazoline, and 0.0% of alkyl halide is added as a catalyst. 1% to 1.0% by weight is mixed, and to this is added a filler with an average aspect ratio of 5 or more and 20 or less, and a spherical, flake, or fibrous filler with an average aspect ratio of 1 or more and 3 or less.
A reaction molding resin composition mixed in an amount of at least 60% by weight. (3) Oxazoline is used as liquid A, guanamine or heterocyclic amine having a spiroacetal ring is mixed in a molar ratio of 1.0 to 2.0 with respect to oxazoline, and 0.00% of alkyl halide is added as a catalyst. A mixture of 1% to 1.0% by weight is called liquid B, and the liquid A and B are
A method for molding a reaction-molded resin composition, which comprises heating the respective liquids and injecting them into a mixing head to mix them, and then injecting them into a mold in a vacuum chamber to form a molded article. .