JPS6031204B2 - Unsaturated vinyl ester resin thickening composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an unsaturated vinylester resin thickening composition that has excellent heat resistance, water resistance, and thickening properties.

In general, resins used in the production of FRP products such as SMC and BMC are required to have excellent thickening properties in order to facilitate film release and workability during molding, and to obtain good impregnation properties. Ru. On the other hand, recently, FRP products are required to have better properties such as heat resistance, water resistance, and corrosion resistance than conventional products had. However, recently, with the spread of solar systems, more than 9,500 types of hot water can now be stored in tanks. Therefore, in order to satisfy these characteristics, a method using an unsaturated vinyl ester resin and an isocyanate compound has been proposed, but an unsaturated vinyl ester resin was obtained using a diglycidyl ether type epoxy resin of bisphenol A. case,
Since the diglycidyl ether type epoxy resin of pisphenol A has a chain structure, the cured product of unsaturated vinyl ester resin is significantly degraded by hot water at 9500 or higher.
Further, although the unsaturated vinyl ester resin obtained using a bisphenol A diglycidyl ether type epoxy resin having an average molecular weight of 900 or more has good thickening properties, the final thickening degree varies widely. Unsaturated vinyl ester resins obtained using bisphenol A diglycidyl ether type epoxy resins having an average molecular weight of 700 or less have a low molecular weight and therefore have poor thickening properties, and furthermore, the final thickening degree varies widely. 4. In order to prevent the deterioration of cured resin products due to hot water at 95 oo or more, we used a polyglycidyl ether type epoxy resin of phenol formaldehyde novolac instead of the diglycidyl ether type epoxy resin of bisphenol A. When used, the deterioration of the resulting cured unsaturated vinylester resin due to hot water of 95o0 or higher is reduced, but the unsaturated vinylester resin contains fewer hydroxyl groups and its molecular structure has a chain structure. Therefore, it has disadvantages such as poor thickening properties and large variations in the final thickening degree. The present invention provides an unsaturated vinyl ester resin thickening composition that eliminates the above-mentioned drawbacks, and as a result of extensive research, the present inventors have found that the average molecular weight is 9.
In the case of an unsaturated vinyl ester resin using diglycidyl ether type epoxy resin of bisphenol A of 00 or more, it has poor heat resistance, water resistance, and corrosion resistance, but has excellent thickening properties, and has an average molecular weight of 600 or more. In the case of an unsaturated vinyl ester resin using a simple polyglycidyl ether type epoxy resin, it has poor thickening properties but has excellent heat resistance, water resistance, and corrosion resistance, and when lithium chloride is used as an addition catalyst, the final viscosity increase When the variation in 3-
It was found that when methyl isocyanate-3,5,5-trimethylcyclohexyl isocyanate was used, the initial rate of increase was slow and the final thickening was the same as when using other polyisocyanate compounds, By combining these technologies, we have completed the invention of an unsaturated vinylester resin composition that has excellent heat resistance, water resistance, corrosion resistance, and thickening properties, and can be manufactured industrially easily and inexpensively. .

The present invention is based on glycidyl ether type epoxy resin of bisphenol A having an average molecular weight of 900 or more and an average molecular weight of 6
00 or more phenol formaldehyde novolak polyglycidyl ether type epoxy resin {B} and molar ratio W/'B} of 0.5/0.5 to 0.01/0.99
Reactant (1) obtained by reacting epoxy resin containing methacrylic acid with methacrylic acid in the presence of lithium chloride, styrene (0) and 3-isocyanate methyl-3,5,5-
The present invention relates to an unsaturated vinyl ester resin thickening composition containing trimethylcyclohexyl isocyanate (m).

Examples of bisphenol A glycidyl ether type epoxy resins having an average molecular weight of 900 or more used in the present invention include Epicoat 1001, 1004, and 10 manufactured by Kagaku Co., Ltd.
07, 1009, etc., and as a polyglycidyl ether type epoxy resin of phenol formaldehyde novolak having an average molecular weight of 600 or more, for example, D. E. Examples include N438 and 439. The glycidyl ether type epoxy resin style of pisphenol A with an average molecular weight of 900 or more and the polyglycidyl ether type epoxy resin of phenol formaldehyde novolak with an average molecular weight of 600 or more [B} are used to improve the heat resistance, water resistance, Based on corrosion resistance and thickening properties, the molar ratio is
B} is used with 0.5/0.5 to 0.01/0.99. It is preferable to use methacrylic acid in an amount of 0.9 to 1.1 equivalents per 1 equivalent of epoxy in the epoxy resin. Lithium chloride is used as an addition catalyst, but it is preferably used in an amount of 0.1 to 5% by mass based on the total amount of epoxy resin and methacrylic acid.

3-Isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (Germany, VEBA-C
Manufactured by HEMIEAG, isophoron di-socyanate, I
The amount of PDI) used is 0 for the above reactants and styrene.
．． It is preferable to use styrene in a range of 5 to 30% by mass, and it is preferable to use styrene in a range of 10 to 80% by mass based on the above reactants.

The thickening composition of the present invention may optionally contain inorganic fillers such as calcium carbonate and aluminum hydroxide, organic peroxides such as methyl methyl ketone peroxide and t-phthyl peroxybenzoate, polyethylene and polystyrene. , thermoplastic resins such as polyvinyl acetate, and the like.

The unsaturated vinyl ester resin thickening composition of the present invention has a very slow thickening property at the initial stage compared to the secondary composition, so it has good impregnability into fibers and workability, and the cured product has good heat resistance. Excellent water resistance and mechanical properties.

Examples will be described in detail below, but the present invention is not limited thereto.

In the examples, parts refer to parts by mass. Example 1 Epiquat 100,145 parts (0.05 mol), DEN4
38,612 parts (0.95 mol) and methacrylic acid 303 (
3.52 mol) parts in the presence of 9.6 parts of lithium chloride.
The reaction was carried out at 0oC, and when the acid value of the reactant reached 4.0, heating was stopped and the reaction was set at the end point.

21 parts of this reaction product and 9 parts of styrene were added and dissolved to obtain an unsaturated vinyl ester resin. To 100 parts of this unsaturated vinyl ester resin, calcium carbonate (Nippon Funka Co., Ltd., N
After adding 150 parts of S-200) and 17 parts of IPD and stirring uniformly, use a BL type rotational viscometer (manufactured by Seiki Kogyo Kenkyusho) at 2300 for 10 to 180 minutes and an HBT type rotational viscometer for 1 to 7 days. (manufactured by Brookfield) to measure changes in viscosity over time. The results are shown in Table 1. In addition, 2 parts of methyl ethyl ketone peroxide (Nippon Oil Co., Ltd., Permec N) was added to 10 parts of unsaturated vinyl ester resin, and after uniformly molding, it was molded into a 127 x 12.7 x 1 HDT mold. HDT (heating strain temperature) of a test piece that was left at 2300°C for 2 hours and then after-cured at 120°C for 18 hours.
was measured according to ASTM D648. The results are shown in Table 1. Example 2 Epicote 10019 anchor (0-1 mol), DEN43
8580 parts (0.9 mol) and 296 parts (3 mol) of methacrylic acid.
．． 44 mol) in the presence of 9.66 parts of lithium chloride.
The reaction was carried out at 0:00 pm, and since the acid value of the reactant reached 4.2, heating was stopped and the reaction was set as the end point.

After adding 2 parts of methyl ethyl ketone peroxide to the unsaturated vinyl ester resin dissolved by adding 8 parts of this reaction product and 2 parts of styrene to form a uniform layer, a test piece was prepared in the same manner as in Example 1. was measured. The results are shown in Table 1. Example 3 49 parts of the reactant used in Example 2 and 21 parts of styrene were added and dissolved to obtain an unsaturated vinyl ester resin.

Three pieces were prepared by adding 150 parts of calcium carbonate to 100 parts of this unsaturated vinyl ester resin, and the IPDI was 6.
5 copies, 7.0 copies or? ．． After adding 5 parts and stirring uniformly, the change in viscosity over time was measured in the same manner as in Example 1. The results are shown in Table 1. In addition, unsaturated pinyester resin 10
After adding 2 parts of methyl ethyl ketone peroxide to the mixture and stirring it uniformly, a test piece was prepared in the same manner as in Example 1, and HDT was measured. The results are shown in Table 1. Example 4 2 parts of methyl ethyl ketone peroxide was added to the unsaturated vinyl ester resin obtained by adding 6 anchor parts of the reactant obtained in Example 2 and 4 parts of styrene and melted, and the mixture was uniformly mixed into a rope using the same method as in Example 1. A test piece was prepared and HDT was measured.

The results are shown in Table 1. Example 5 Epiquat 1001 135 parts (0.15 mol), DE
N438548 parts (0.85 mol) and methacrylic acid 28
9 parts (3.36 moles) were reacted in the presence of 9.6 parts of lithium chloride at 8,000 ℃, and when the acid value of the reactant reached 3.9, heating was stopped to mark the end of the reaction.

21 parts of this reaction product and 9 parts of styrene were added and dissolved to obtain an unsaturated vinyl ester resin. 150 parts of unsaturated vinyl ester resin, 150 parts of calcium carbonate, IPD
After adding 17 parts and stirring uniformly, the change in viscosity over time was measured in the same manner as in Example 1. The results are shown in Table 1. Further, 2 parts of methyl ethyl ketone peroxide was added to 10 parts of unsaturated vinyl ester resin and mixed uniformly, and then a test piece was prepared in the same manner as in Example 1, and HDT was measured.
The results are shown in Table 1. Comparative Example 1 Epicote 82838 base (1 mol) and methacrylic acid 1
72 (2 mol) was reacted in the presence of 5.52 parts of lithium chloride at 80 mm, and when the acid value of the reactant reached 4.0, heating was stopped and the reaction was taken as the end point. 8 Seiko styrene 2 sparse portion was added and dissolved to obtain an unsaturated vinyl ester resin.

After adding 2 parts of methyl ethyl ketone peroxide to this unsaturated vinyl ester resin and stirring it uniformly, a test piece was prepared in the same manner as in Example 1, and HDT was measured. The results are shown in Table 1. Comparative Example 2 To the reactant 28 used in Comparative Example 1, 12 parts of styrene was added and dissolved to obtain an unsaturated vinylester resin.

Three pieces were prepared by adding 150 parts of calcium carbonate to 100 parts of this unsaturated vinyl ester resin, and the DI was 6.5.
After adding 7.0 parts or 7.5 parts and worshiping it evenly,
Changes in viscosity over time were measured in the same manner as in Example 1. The results are shown in Table 1. Further, 10 parts of unsaturated vinyl ester resin and 2 parts of methyl ethyl ketone peroxide were added and mixed uniformly, and a test piece was prepared in the same manner as in Example 1, and HDT was measured. The results are shown in Table 1. Comparative Example 3 2 parts of methyl ethyl ketone peroxide was added to the unsaturated vinyl ester resin which had been dissolved by adding the reactant 6, the styrene 4, and the base used in Comparative Example 1, and then the same method as in Example 1 was carried out. A test piece was prepared and HDT was measured.

The results are shown in Table 1. Comparative Example 4 The catalyst of Example 2 was
The reaction was carried out at 80qo instead of 2,4,6-dimethylaminomethylphenol (manufactured by Shikoku Kasei, DMP-30).
Since the acid value of the reactant reached 4.1, heating was stopped and the reaction was determined to be at the end point.

Add and dissolve 7 parts of this reactant, 3 parts of styrene, 15 parts of calcium carbonate, and 17 parts of IPD. After adding and stirring uniformly, the change in viscosity over time was measured in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 5 Three samples were prepared by adding 15 parts of calcium carbonate to 100 parts of the unsaturated vinyl ester resin obtained in Example 3, and diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Co., Ltd.) was prepared.
6.5 parts of Millionate MT), 7. After adding 7.5 parts of the base and spreading it uniformly, the change in viscosity over time was measured in the same manner as in Example 1.

The results are shown in Table 1. Table 1 As is clear from Table 1, the unsaturated vinyl ester resin thickening composition of the present invention has excellent heat resistance, and exhibits an initial increase in viscosity when reacted with 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate. It is suitable as a resin lees thickening composition for SMC and BMC because it has a gentle impregnating property into fibers, and has extremely excellent thickening properties with little variation in the final thickening degree.

Claims (1)

[Claims] 1 Glycidyl ether type epoxy resin (A) of bisphenol A with an average molecular weight of 900 or more and an average molecular weight of 60
0 or more phenol formaldehyde novolak polyglycidyl ether type epoxy resin (B) and molar ratio (A)/(B) of 0.5/0.5 to 0.01/0.9
Reactant (I) obtained by reacting the epoxy resin contained as 9 with methacrylic acid in the presence of lithium chloride, styrene (II) and 3-isocyanate methyl-3, 5, 5
- An unsaturated vinyl ester resin thickening composition containing trimethylcyclohexyl isocyanate (III).