JPH0826117B2 - Unsaturated vinyl ester resin composition and thickening composition thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to an unsaturated vinyl ester resin composition and a thickening composition thereof, and more specifically, an unsaturated vinyl excellent in heat resistance, hot water resistance and thickening property. The present invention relates to an ester resin composition and a thickening composition thereof.

[Conventional technology]

Generally, resins used in FRP products such as SMC and BMC are required to have excellent thickening properties in order to obtain film peeling property during molding, workability and impregnation property, and more recently, heat resistance, hot water resistance and corrosion resistance. Are required to have better characteristics than before. For example, in the case of tanks, water or warm water of about 60 ° C was conventionally stored, but recently, with the spread of the solar system, hot water of 95 ° C or higher has been stored in the tank, which makes it more resistant to heat. A product is required.

In order to solve these problems, a method using an unsaturated vinyl ester resin and an isocyanate compound has been proposed. However, a cured product of an unsaturated vinyl ester resin obtained by using a bisphenol A diglycidyl ether type epoxy resin has a chain structure of the bisphenol A diglycidyl ether type epoxy resin.
There is a drawback that deterioration due to hot water at temperatures above ℃ becomes large. Further, although the unsaturated vinyl ester resin obtained by using a diglycidyl ether type epoxy resin of bisphenol A having an average molecular weight of 900 or more has a good viscosity increase, the final viscosity increase varies widely. Further, the unsaturated vinyl ester resin obtained by using a diglycidyl ether type epoxy resin of bisphenol A having an average molecular weight of 700 or less has a drawback that the viscosity increase is poor because the molecular weight is small and the final viscosity increase varies.

On the other hand, although the deterioration of the unsaturated vinyl ester resin cured product obtained by using the polyglycidyl ether type epoxy resin of phenol formaldehyde novolac by hot water of 95 ° C or higher is small, the unsaturated vinyl ester resin contains few hydroxyl groups, Since the molecular structure does not have a chain structure, it has disadvantages such as poor viscosity increase and large variation in final viscosity increase.

Furthermore, in Japanese Patent No. 1307124, a glycidyl ether type epoxy resin of bisphenol A having an average molecular weight of 900 or more and a polyglycidyl ether type epoxy resin of phenol formaldehyde novolac having an average molecular weight of 600 or more are reacted with methacrylic acid in the presence of lithium chloride. A method using an unsaturated vinyl ester resin thickening composition containing styrene and 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate in the obtained reaction product is shown.

However, although the composition has improved heat resistance, water resistance and thickening property, the reaction rate is slow since lithium chloride is used as the addition catalyst, and gelation is likely to occur due to a long reaction time. Further, the storage stability of the obtained reaction product is poor, and there is a problem that the viscosity increase and the final viscosity increase vary from lot to lot.

[Problems to be Solved by the Invention]

An object of the present invention is to solve the above-mentioned problems of the prior art, to provide an unsaturated vinyl ester resin composition and a thickening composition thereof which are excellent in heat resistance, hot water resistance, corrosion resistance and thickening property and which are easy to industrially manufacture. It is provided.

[Means for solving the problem]

MEANS TO SOLVE THE PROBLEM As a result of earnest research to solve the above-mentioned problems, the present inventors have found that a bisphenol A diglycidyl type epoxy resin having an average molecular weight of 900 or more and a phenol formaldehyde novolac polyglycidyl ether type epoxy resin having an average molecular weight of 600 or more are used. Is used in a specific amount,
The unsaturated vinyl ester resin obtained by reacting this with methacrylic acid is excellent in thickening, heat resistance, hot water resistance and corrosion resistance, and tri-2,4,6-dimethylaminomethylphenol is used as an addition catalyst. The reaction speed is fast, gelation does not occur during the reaction, the resulting unsaturated vinyl ester resin has excellent storage stability, and the thickening and final thickening do not vary among lots. It was found that when 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate is used as the polyisocyanate compound that is a component of the viscous composition, the initial thickening speed is slow and the final thickening variation is small. The present invention has been completed.

That is, the first aspect of the present invention is to provide a glycidyl ether type epoxy resin (a) of bisphenol A having an average molecular weight of 900 or more and a polyglycidyl ether type epoxy resin (b) of phenol formaldehyde novolac having an average molecular weight of 600 or more (a). ) / (B) molar ratio is 0.5 / 0.5-0.0
An epoxy resin containing 1 / 0.99 and methacrylic acid are reacted in the presence of tri-2,4,6-dimethylaminomethylphenol to give a reaction product (I) and styrene. It relates to a saturated vinyl ester resin composition.

A second aspect of the present invention relates to an unsaturated vinyl ester resin thickening composition, which further comprises 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate in the unsaturated vinyl ester resin composition.

Examples of the glycidyl ether type epoxy resin (a) of bisphenol A having an average molecular weight of 900 or more used in the present invention include commercially available Epicoat 1001, 1004,
1007, 1009 (trade name of Shell Chemical Co., Ltd.) and the like can be used.

As the polyglycidyl ether type epoxy resin (b) of phenol formaldehyde novolac having an average molecular weight of 600 or more used in the present invention, for example, commercially available DEN438, 439 (trade name of Dow Chemical Co.) can be used.

From the viewpoint of heat resistance, hot water resistance, corrosion resistance and thickening of the cured product, the epoxy resin (a) and the epoxy resin (b) are used in a molar ratio of (a) / (b) of 0.5 / 0.5 to
The range is 0.01 / 0.99.

The reaction product (I) in the present invention uses the epoxy resins (a) and (b) in the above-mentioned mixing ratio, and methacrylic acid is added to the addition catalyst of tri-2,4,6-dimethylaminomethylphenol. It is obtained by reacting in the presence.

The amount of methacrylic acid used is preferably 0.9 to 1.1 equivalents relative to 1 equivalent of epoxy of the epoxy resin. Further, tri-2,4,6-dimethylaminomethylphenol is represented by the following structural formula, It is preferable to use it in the range of 0.1 to 5% by weight based on the total amount of epoxy resin and methacrylic acid.

The unsaturated vinyl ester resin composition of the present invention is obtained by dissolving the reaction product (I) in styrene, and the amount of the styrene used is in the range of 10 to 80% by weight based on the reaction product (I). Is preferably used in.

The unsaturated vinyl ester resin thickening composition of the present invention is the above-mentioned unsaturated vinyl ester resin composition, which is represented by the following structural formula: 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate. It is obtained by containing. Examples of this isocyanate compound include isophorone diisocyanate IPDI (hereinafter referred to as IPDI) manufactured by VEBA-CHEMIE AG (Germany),
The amount used is preferably in the range of 0.5 to 30% by weight based on the total amount of the reaction product (I) and styrene.

The thickening composition, if necessary, calcium carbonate, an inorganic filler such as aluminum hydroxide, glass fiber,
Fiber reinforcing material such as carbon fiber, thermoplastic resin such as polystyrene, polyethylene, polyvinyl acetate, polybutadiene-styrene copolymer, organic peroxide such as methyl ethyl ketone peroxide, benzoyl peroxide, t-butyl peroxybenzoate, dimethyl. Curing accelerators such as aniline, cobalt octenoate, cobalt naphthenate,
A release agent such as zinc stearate, a hydroquinone, a polymerization inhibitor such as p-benzoquinone, a coloring agent, and the like may be contained.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples. In the examples, “parts” means “parts by weight”.

Example 1 Epicoat 1001, 90 parts (0.1 mole) and DEN438, 580
Parts (0.9 mol) and 296 parts of methacrylic acid (3.44 mol),
The reaction was carried out at 80 ° C. in the presence of 7.25 parts of tri-2,4,6-dimethylaminomethylphenol and 1.0 part of 2,5-diphenyl-p-benzoquinone. Four hours after the start of the reaction, the acid value of the reaction product reached 10.4, so heating was stopped and the reaction was terminated. To 210 parts of this reaction product, 90 parts of styrene was added and dissolved,
An unsaturated vinyl ester resin composition was obtained.

The unsaturated vinyl ester resin composition was sealed in a glass test tube, and the time (stability) until gelation was measured in an oil bath at 100 ° C.

Also, to 100 parts of this unsaturated vinyl ester resin composition,
After adding 2 parts of methyl ethyl ketone peroxide (Permek N, manufactured by NOF CORPORATION) and 0.5 part of a styrene solution of dimethylaniline (10 parts of dimethylaniline, 90 parts of styrene) and uniformly stirring, 127 × 12.7 × 6.35 mm ^t HDT ( Heat strain temperature) H of the test piece cast in a mold for a test piece, left at 23 ° C for 24 hours, and aftercured at 120 ° C for 18 hours.
DT was measured according to ASTM D648.

Furthermore, 100 parts of unsaturated vinyl ester resin composition, 150 parts of calcium carbonate (NS-200, manufactured by Nitto Koka) and IPDI
After 8.5 parts were added and the mixture was stirred uniformly, the change in viscosity with time was measured at 23 ° C. The viscosity is measured with an HB type rotational viscometer (manufactured by Brookfield) from 30 to 180 minutes, and thereafter the viscosity is an HBT type rotational viscometer (manufactured by Brookfield).
It was measured at. The results are shown in Table 1.

Example 2 Epicoat 1001, 45 parts (0.05 mol) and DEN438, 61
2 parts (0.95 mol) and methacrylic acid 303 parts (3.52 mol) were added to tri-2,4,6-dimethylaminomethylphenol 7.2.
Parts and 0.96 parts of 2,5-diphenyl-p-benzoquinone. Four hours after the start of the reaction, the acid value of the reaction product reached 10.1, so heating was stopped and the reaction was terminated. To 120 parts of this reaction product, 30 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition. The stability of this unsaturated vinyl ester resin composition, HDT, was determined in Example 1.
It measured by the method similar to. The results are shown in Table 1.

Example 3 To 490 parts of the reaction product used in Example 2, 210 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition. Three parts were prepared by adding 150 parts of calcium carbonate to 100 parts of this unsaturated vinyl ester resin composition, and IPDI 8.0 parts, 8.5 parts
And 9.0 parts were added and stirred uniformly, and the change in viscosity with time was measured by the same method as in Example 1. 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 To 60 parts of the reaction product obtained in Example 2 and 40 parts of styrene was added and dissolved, to an unsaturated vinyl ester resin composition, 2 parts of methyl ethyl ketone peroxide and 0.5 part of a styrene solution of dimethylaniline were added and stirred uniformly. Example 1
A test piece was prepared by the same method as described above, and HDT was measured. The results are shown in Table 1.

Example 5 Epicoat 1001, 135 parts (0.15 mol) and DEN438, 5
48 parts (0.85 mol) and 289 parts of methacrylic acid (3.36 mol) were added at 80 ° C. in the presence of 7.3 parts of tri-2,4,6-dimethylaminomethylphenol and 0.97 part of 2,5-diphenyl-p-benzoquinone. The reaction was carried out. Four hours after the start of the reaction, the acid value of the reaction product reached 9.8, so heating was stopped and the reaction was terminated. To 210 parts of this reaction product, 90 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition. The stability of this unsaturated vinyl ester resin composition was measured by the same method as in Example 1. Unsaturated vinyl ester resin composition
After adding 150 parts of calcium carbonate and 8.5 parts of IPDI to 100 parts and stirring uniformly, the change with time of viscosity was measured by the same method as in Example 1. Further unsaturated vinyl ester resin composition
After adding 2 parts of methyl ethyl ketone peroxide and 0.5 part of a styrene solution of dimethylaniline to 100 parts and stirring 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 6 In order to confirm reproducibility, the reaction was carried out under the same formulation and reaction conditions as in Example 2, and 4 hours after the start of the reaction, the acid value was 10.2.
Therefore, the heating was stopped and the reaction was terminated. To 210 parts of this reaction product, 90 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition. The stability, HDT, and viscosity change with time of this unsaturated vinyl ester resin composition were measured by the same method as in Example 1. The results are shown in Table 1.

Comparative Example 1 DEN438, 644 parts (1.0 mol) and methacrylic acid 310 parts (3.6
Mol) and 7.2 parts of tri-2,4,6-dimethylaminomethylphenol and 2,5-diphenyl-p-benzoquinone.
The reaction was carried out at 90 ° C in the presence of 95 parts. Four hours after the start of the reaction, the acid value of the reaction product reached 10.1, so heating was stopped and the reaction was terminated. To 210 parts of this reaction product, 90 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition.
The stability, viscosity change with time, and HDT of this unsaturated vinyl ester resin composition were measured in the same manner as in Example 1.
The results are shown in Table 2.

Comparative Example 2 Epicoat 1001, 495 parts (0.55 mol) and DEN438, 2
90 parts (0.45 mol) and 234 parts of methacrylic acid (2.72 mol) at 80 ° C. in the presence of 7.6 parts of tri-2,4,6-dimethylaminomethylphenol and 1.0 part of 2,5-diphenyl-p-benzoquinone. The reaction was carried out. Four hours after the start of the reaction, the acid value of the reaction product reached 9.9, so heating was stopped and the reaction was terminated. To 210 parts of this reaction product, 90 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition. The stability, viscosity change with time, and HDT of this unsaturated vinyl ester resin composition were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 3 Epicoat 1001, 900 parts (1 mol) and methacrylic acid 172
Parts (2 moles) were reacted at 80 ° C. in the presence of 8.0 parts of tri-2,4,6-dimethylaminomethylphenol and 1.1 parts of 2,5-diphenyl-p-benzoquinone. Four hours after the start of the reaction, the acid value of the reaction product reached 9.8, so heating was stopped and the reaction was terminated. Styrene 90 in 210 parts of this reaction product
Parts were added and dissolved to obtain an unsaturated vinyl ester resin composition. The stability of this unsaturated vinyl ester resin composition,
The change in viscosity with time and HDT were measured by the same method as in Example 1. The results are shown in Table 2.

Comparative Example 4 Epicoat 828, 380 parts (1 mol) and methacrylic acid 172
Part (2 mol) was reacted at 80 ° C. in the presence of 4.1 parts of tri-2,4,6-dimethylaminomethylphenol and 0.55 part of 2,5-diphenyl-p-benzoquinone. Four hours after the start of the reaction, the acid value of the reaction product reached 10.1, so heating was stopped and the reaction was terminated. Styrene 90 in 210 parts of this reaction product
Parts were added and dissolved to obtain an unsaturated vinyl ester resin composition. The stability of this unsaturated vinyl ester resin composition,
The change in viscosity with time and HDT were measured by the same method as in Example 1. The results are shown in Table 2.

Comparative Example 5 Epicoat 1001, 45 parts (0.05 mol) and DEN438, 61
2 parts (0.95 mol) and methacrylic acid 303 parts (3.52 mol) were reacted at 80 ° C. in the presence of 9.6 parts of lithium chloride and 0.96 parts of 2,5-diphenyl-p-benzoquinone. 26 hours after the start of the reaction, the acid value reached 4.0, so heating was stopped and the reaction was terminated. To 210 parts of this reaction product, 90 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition.
Stability and HD of this unsaturated vinyl ester resin composition
T was measured by the same method as in Example 1. The results are shown in Table 2.

Comparative Example 6 Reaction was carried out under the same formulation and reaction conditions as in Comparative Example 5,
The acid value reached 10.8 within 15 hours after the start of the reaction, so heating was stopped and the reaction was terminated. Styrene 90 in 210 parts of this reaction product
Parts were added and dissolved to obtain an unsaturated vinyl ester resin composition. The stability of this unsaturated vinyl ester resin composition,
The change in viscosity with time and HDT were measured by the same method as in Example 1. The results are shown in Table 2.

Comparative Example 7 Epicoat 1001, 45 parts (0.05 mol) and DEN438, 61
2 parts (0.95 mol) and 303 parts of methacrylic acid (3.52 mol) were combined with 9.6 parts of dimethyl sulfide and 2,5-diphenyl-p-
The reaction was carried out at 80 ° C. in the presence of 0.96 part of benzoquinone, and 2 hours after the start of the reaction, the acid value became 1.03, so heating was stopped and the reaction was terminated. To 210 parts of this reaction product, 90 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition. The stability and HDT of this unsaturated vinyl ester resin composition were measured by the same method as in Example 1. The results are shown in Table 2.

Comparative Example 8 The reaction was carried out in the same manner as in Comparative Example 7 except that dimethyl sulfide of Comparative Example 7 was changed to pyridine, and the acid value became 10.1 within 2 hours after the start of the reaction, so heating was stopped and the reaction was terminated. To 210 parts of this reaction product, 90 parts of styrene was added and dissolved,
An unsaturated vinyl ester resin composition was obtained. The stability, viscosity change with time, and HDT of this unsaturated vinyl ester resin composition were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 9 The reaction was carried out in the same manner as in Comparative Example 7 except that the dimethyl sulfide of Comparative Example 7 was changed to triethylamine, and the acid value reached 10.2 4 hours after the start of the reaction, so heating was stopped and the reaction was terminated. To 210 parts of this reaction product, 90 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition. The stability, viscosity change with time, and HDT of this unsaturated vinyl ester resin composition were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 10 The reaction was carried out in the same manner as in Comparative Example 7 except that the dimethyl sulfide of Comparative Example 7 was changed to tetramethylammonium chloride, and the acid value became 10.2 1.5 hours after the start of the reaction, so heating was stopped and the reaction was terminated. And To 210 parts of this reaction product, 90 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition. The stability and HDT of this unsaturated vinyl ester resin composition were measured by the same method as in Example 1.
The results are shown in Table 2.

Comparative Example 11 The reaction was performed in the same manner as in Comparative Example 7 except that p-toluenesulfonic acid was used instead of dimethyl sulfide of Comparative Example 7.
No decrease in acid value was observed even 15 hours after the start of the reaction.

Comparative Example 12 To 105 parts of the reaction product used in Example 2, 45 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition. To 100 parts of this unsaturated vinyl ester resin composition was added 150 parts of calcium carbonate and 8.5 parts of methylenebis-4-phenylisocyanate (trade name: Isonate 143L manufactured by Upjohn Polymer Chemicals), and the mixture was stirred uniformly and then the same method as in Example 1 was performed. The change in viscosity with time was measured with. The results are shown in Table 2.

Comparative Example 13 To 105 parts of the reaction product used in Example 2, 45 parts of styrene was added and dissolved to obtain an unsaturated vinyl ester resin composition. To 100 parts of this unsaturated vinyl ester resin composition, 150 parts of calcium carbonate and 8.5 parts of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., HMD I) were added and stirred uniformly, and then the viscosity was changed with time by the same method as in Example 1. It was measured.
The results are shown in Table 2.

From Tables 1 and 2, the unsaturated vinyl ester resin composition of the present invention is excellent in stability and heat resistance, and its thickening composition is 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate. It is shown that in the reaction (1), the increase in viscosity in the initial stage is slow, the impregnation property to the fiber is good, and further, the final viscosity increase and the variation in the resin lot are small, and the viscosity increase is extremely excellent.

[Effects of the Invention] The unsaturated vinyl ester resin composition of the present invention is excellent in stability during reaction and storage stability. Further, the thickening of the thickening composition is very gentle in the initial stage, so that the ability to impregnate fibers and workability are good, and the variation in the final thickening is small, and the cured product has heat resistance, hot water resistance, and Excellent mechanical properties. Therefore, the thickening composition of the present invention, SMC and B
It is useful for FRP products such as MC.

Claims (2)

[Claims] 1. A glycidyl ether type epoxy resin (a) of bisphenol A having an average molecular weight of 900 or more and a polyglycidyl ether type epoxy resin (b) of phenol formaldehyde novolac having an average molecular weight of 600 or more (a) / ( An epoxy resin containing b) in a molar ratio of 0.5 / 0.5 to 0.01 / 0.99 and methacrylic acid are added to tri-2,4,6-
An unsaturated vinyl ester resin composition comprising a reaction product (I) obtained by reacting in the presence of dimethylaminomethylphenol and styrene. 2. An unsaturated vinyl ester resin thickening composition comprising the unsaturated vinyl ester resin composition according to claim 1 and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate.