JPH0153965B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition with excellent thickening properties that is extremely useful for applying molding methods such as sheet molding compound method and bulk molding compound method. In the sheet molding compound method, etc., a thickener such as magnesium oxide is added to an unsaturated polyester resin compound to cause a reaction between the terminal carboxyl group of the resin and the magnesium oxide, a so-called thickening reaction, to make the compound sticky. Get no compound. However, vinyl ester resin obtained by reacting an epoxy resin with an unsaturated monobasic acid does not have a carboxyl group that reacts with magnesium oxide, so it has been impossible to use it in sheet molding compound methods, etc. . For this reason, attempts have been made in the past to add carboxyl groups to vinyl ester resins. The first method is to react one equivalent of an epoxy resin with one equivalent of a terminally unsaturated monobasic acid, and then react with a polybasic acid such as maleic acid. However, in this case, a sufficient thickening reaction is not shown, and when the number of equivalents of the polybasic acid to be reacted is increased,
The disadvantage is that it tends to gel during synthesis. The second method is a method of reacting polyester oligomers. Examples of such oligomers include those having carboxyl groups at both ends, such as maleic acid-propylene glycol-maleic acid. As a reaction method, a method has been proposed in which less than 1 equivalent of an unsaturated monobasic acid is reacted with 1 equivalent of epoxy resin, and then the remaining epoxy is reacted with an oligomer to impart carboxyl to the terminal. However, with this method, gelation during synthesis was extremely rare, but only a low viscosity thickening reaction was shown, and when the number of equivalents of oligomers to be reacted was increased, the proportion of polyester oligomers increased, A disadvantage has arisen in that the properties of vinyl ester resins, such as strength and corrosion resistance, are impaired. The present invention was made with the aim of providing a resin that exhibits excellent thickening properties without impairing the properties such as strength and corrosion resistance of vinyl ester resin, and it is possible to obtain a resin that exhibits excellent thickening properties by using a special unsaturated ester. The purpose has been achieved. (A) 1.0 equivalent of bisphenol epoxy resin or novolac epoxy resin and 1.0 equivalent of unsaturated monobasic acid.
After reacting less than an equivalent amount, polyfunctional alcohol and one or more of maleic acid, maleic anhydride, and fumaric acid (hereinafter referred to as maleic acid, etc.)
and (B) a polymerizable monomer. As the epoxy resin, bisphenol epoxy resin or novolak epoxy resin may be used alone or in combination of two or more. Bisphenol epoxy resins, for example, have the general formula [In the formula, x represents an integer of 0 to 15]. Commercially available bisphenol epoxy resins include Epicote 828, Epicote 1001, Epicote 1004 manufactured by Ciel Chemical Co., Ltd., and AER manufactured by Asahi Kasei Corporation.
Examples include -664H, AER-331, AER337, DER330, DER660, DER664 manufactured by Dow Chemical Company. It is also possible to use products in which some of the hydrogen atoms are replaced with halogens (for example, bromine), such as Epotote YDB-340 and YDB400 commercially available from Toto Kasei Co., Ltd. Novolac epoxy resin, for example, has the general formula: [In the formula, R ₁ , R ₂ and R ₃ are hydrogen or an alkyl group, and they may be the same or different, and y represents an integer of 0 to 15].
Commercially available products belonging to this type of novolac epoxy resin include, for example, DEN431 manufactured by Dow Chemical Company,
Examples include DEN438, Epicote 152 and Epicote 154 manufactured by Ciel Chemical Co., Ltd., and EPN1138 manufactured by Ciba Geigy. Examples of unsaturated monobasic acids to be reacted with the epoxy resin include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and tricyclo[5,2,1,0 ^2,6 ]-4
Partially esterified carboxylic acids containing decene-8 or -9 residues and unsaturated dibasic acid residues as constituent elements can be used. Examples of partially esterified carboxylic acids include 8- or 9-hydroxytricyclodecene-4-(5,2,1,0 ^2,6 ) 1.00 to
There is an unsaturated dibasic acid monoester obtained by heating 1.20 mol of maleic anhydride and 1 mol of an unsaturated dibasic acid such as maleic anhydride, itaconic acid, traconic acid at 70 to 150°C under a stream of inert gas. Epoxy resin and unsaturated monobasic acid are usually
The reaction is carried out by heating to a temperature of 60 to 150°C, preferably 70 to 130°C. In order to leave unreacted epoxy groups, the unsaturated monobasic acid is reacted in a proportion of less than 1 equivalent, preferably 0.60 to 0.95 equivalent, per equivalent of epoxy resin. The reaction is preferably allowed to proceed until the acid value reaches a low value of 20 or less, and in order to prevent gelation due to polymerization during the reaction,
It is preferable to add a polymerization inhibitor such as hydroquinone, di-tert-butylcatechol, and parabenzoquinone. Furthermore, during this esterification reaction, quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, tertiary amines such as triethylamine and dimethylaniline, ferric chloride, lithium hydroxide, lithium chloride, and tin chloride are used. The reaction time can also be shortened by adding an esterification catalyst such as. In the method of the present invention, after reacting less than 1.0 equivalent of an unsaturated monobasic acid with 1.0 equivalent of the epoxy resin as described above, a polyfunctional alcohol, maleic acid, etc. are added simultaneously or sequentially. As the polyfunctional alcohol, for example, propylene glycol, ethylene glycol, dipropylene glycol, diethylene glycol, neopentyl glycol, hydrogenated bisphenol, glycerin, trimethylolpropane, etc. can be used. Also, if necessary, propanol,
A monohydric alcohol such as butanol can also be used in combination. Maleic acid and the like are reacted together with the polyfunctional alcohol. When reacting these, it is preferable to add polyfunctional alcohol to the reaction product of epoxy resin and unsaturated monobasic acid, stir thoroughly to make it homogeneous, and then add maleic acid. It is also possible to add the functional alcohol and polybasic acid at the same time.
The temperature at the time of addition and the reaction temperature are not particularly limited, but may be the same as the temperature at which the epoxy resin and the unsaturated monobasic acid were reacted, that is, in the temperature range of 60 to 150°C. The amount of maleic acid etc. added is preferably 1 to 4 times equivalent to the remaining epoxy group. If the proportion of maleic acid used exceeds 4 equivalents relative to the remaining epoxy groups, unreacted acid tends to remain, which is undesirable. Moreover, if it is less than the equivalent amount, unreacted epoxy groups tend to remain, resulting in decreased viscosity. The amount of polyfunctional alcohol added is 1.0 maleic acid.
The ratio is preferably 0.10 to 1.00 equivalents. If the amount of polyfunctional alcohol is less than 0.10 equivalent, gelation will easily occur during synthesis;
If the amount exceeds the equivalent amount, unreacted polyfunctional alcohol tends to remain, which is not preferable. Preferred unsaturated esters in the present invention include, for example, 0.60 to 0.95 equivalents of unsaturated monobasic acid and 0.80 equivalent of polyfunctional alcohol per 1.00 equivalent of epoxy resin.
It is an unsaturated ester obtained by reacting ~0.005 equivalent and 0.80 to 0.05 equivalent of a polybasic acid. The polymerizable monomers used in the present invention include:
Examples include styrene, vinyltoluene, chlorostyrene methyl methacrylate, ethyl acrylate, vinyl acetate, p-methylstyrene, α-methylstyrene, and the like. The unsaturated ester which is component (A) in the present invention and
The blending ratio of the polymerizable monomer, component (B), is not particularly limited;
Parts by weight and polymerizable monomers preferably range from 90 to 10 parts by weight. The resin composition of the present invention may further include a thermoplastic resin, an unsaturated polyester resin, a polymerization initiator, a polymerization inhibitor, a reinforcing base material, a filler, a thickener such as magnesium oxide, and a mold release agent. , pigments, and other materials commonly used in sheet or bulk molding compound processes. Next, the present invention will be explained in detail based on examples.
The present invention is not limited to this. In addition,
In the examples, "parts" represent "parts by weight" unless otherwise specified. Example 1 120.4 g (1.40 equivalents) of methacrylic acid, 226.8 g (1.20 equivalents) of bisphenol epoxy resin Epicoat 828 (manufactured by Ciel Chemical Co., Ltd., epoxy equivalent weight 189), Epicoat 1001 (manufactured by Ciel Chemical Co., Ltd., epoxy equivalent weight)
475) 380.0g (0.80 equivalents), 0.20g hydroquinone and 0.05 trimethylbenzylammonium chloride
When heated at 130°C for 7 hours, the acid value decreased to 9. Then propylene glycol 15.2
After mixing for about 10 minutes until homogeneous, 58.8 g (1.20 equivalents) of maleic acid was added and the reaction was continued at 130°C for another 2 hours to form an unsaturated ester with an acid value of 32. Obtained. 65 parts of this unsaturated ester is mixed with 35 parts of styrene containing 0.01 part of hydroquinone.
A resin composition was obtained. Using this resin composition, a compound was prepared according to the formulation shown in Table 1, and its thickening properties were examined.The thickening properties were extremely excellent, and the surface showed no stickiness after 24 hours at 40℃. , that is, the state became tack-free. Comparative Example 1 120.4g (1.40 equivalents) of methacrylic acid, 22.68g
(1.20 eq.) Epicote 828, 380.0 (0.80 eq.)
of Epicote 1001, 0.20 g of hydroquinone and
When 0.05g of trimethylbenzylammonium chloride was heated at 130°C for 7 hours, the acid value decreased to 9. This contains 58.8g of maleic acid (1.20
When an equivalent amount of the resin was added, it immediately gelled and no resin could be produced. Comparative Example 2 69.6g of maleic acid instead of the contained maleic acid
An experiment similar to Comparative Example 1 was conducted except that (1.20 equivalents) was used, but when maleic acid was added, gelation occurred immediately and no resin could be produced. Comparative Example 3 154.8g (1.80 equivalents) of methacrylic acid, 226.8g
(1.20 equivalents) of Epicote 828, 380.0g (0.80 equivalents) of Epicote 1001, 0.20g of hydroquinone, and 0.05g of trimethylbenzylammonium chloride were heated at 130°C for 7 hours, and the acid value was 12.
It dropped to . 23.2 g (0.40 equivalent) of maleic acid was added to this, and the reaction was further carried out at 130°C for 2 hours to obtain an acid value.
18 unsaturated esters were obtained. Add 65 parts of this unsaturated ester to 0.01 parts of hydroquinone.
A resin composition was obtained by dissolving the resin in 35 parts of styrene. Using this resin composition, a compound was prepared with the formulation shown in Table 1, and its thickening properties were examined. It showed low thickening properties, and even after 72 hours at 40°C, it did not become tattle-free. Nakatsuta. Furthermore, when this resin composition was left at 25° C. for two weeks, a phenomenon in which the styrene and the resin separated was observed. Comparative Example 4 192.0 g (2.0 mol) of maleic anhydride and 76.0 g (1.9 mol) of propylene glycol were reacted at 140°C for 2 hours and at 150°C for 1 hour while stirring under a nitrogen stream to form a polyester oligomer with an acid value of 350. Obtained. 120.4g (1.40 equivalents) methacrylic acid, 226.8g
(1.20 equivalents) of Epicote 828, 380.0g (0.80 equivalents) of Epicote 1001, 0.20g of hydroquinone, and 0.05g of trimethylbenzylammonium chloride were heated at 130°C for 7 hours, and the acid value was 9.
It dropped to . Polyester oligomer 192g
(1.20 equivalents) was added, and the reaction was further carried out at 130°C for 2 hours to obtain an unsaturated ester with an acid value of 27. A resin composition was obtained by dissolving 65 parts of the unsaturated ester thus obtained in 35 parts of styrene containing 0.01 part of hydroquinone. Using this resin composition, a compound was prepared according to the formulation shown in Table 1, and its thickening properties were examined. The compound showed low thickening properties, and it took 72 hours to become tack-free. Furthermore, when the mechanical strength of the resin cast product was examined, it was found to be inferior, with low bending strength and bending strain.

【table】

[Table] Example 2 137.6 g (1.60 equivalents) of methacrylic acid, 358 g (2.0 equivalents) of novolac epoxy resin DEN438 (manufactured by Dow Chemical Company, epoxy equivalent weight 179), hydroquinone
When 0.05g and 2.7g of trimethylbenzylammonium chloride were heated at 90°C for 5 hours and 30 minutes,
The acid value decreased to 7. Neopethylene glycol
Add 20.8g (0.40 equivalent) and stir until homogeneous, about 10 minutes.
39.2 g (0.80 g) of maleic anhydride.
(equivalent amount) was added thereto, and the reaction was further carried out at 90°C for 2 hours to obtain an unsaturated ester with an acid value of 24. Add 70 parts of this unsaturated ester to 30 parts of styrene containing 0.01 part of hydroquinone.
A resin composition was obtained. When the thickening properties were examined using the same formulation and method as in Example 1, it showed good thickening properties of 55,000 poise at 40°C for 24 hours, and the tack-free time was 24 hours. Example 3 8- or 9-hydroxytricyclodecene-4
-(5,2,1,0 ^2,6 ) 148.0g (1.0mol) and maleic acid contained 98.0g (1.0mol) were placed under a nitrogen stream.
The mixture was reacted at 150°C for 2 hours to synthesize partially esterified carboxylic acid (dicyclopentadiene maate). 319.8 g (1.30 eq.) dicyclopentadiene maleate, 189.0 g (1.00 eq.) Epicote
828, 475.0 g (1.00 equivalents) of Epicote 1001,
When 0.20 g of hydroquinone and 0.05 g of trimethylbenzylammonium chloride were reacted at 130° C. for 7 hours, the acid value decreased to 11. Add 22.3 g (0.50 equivalents) of trimethylolpropane and mix for approximately 10 minutes until homogeneous, then add maleic acid.
81.2 g (1.40 equivalents) was added and the reaction was further carried out at 130°C for 2 hours to obtain an unsaturated ester with an acid value of 36. 65 parts of this ester was dissolved in 35 parts of styrene containing 0.01 part of hydroquinone to obtain a resin composition. 100.0 parts of this resin composition, 1.0 part of tert-perbenzoate, 4.0 parts of zinc stearate, and 1.0 part of magnesium oxide (#20) were mixed well, and a glass mat (manufactured by Fuji Fiberglass Co., Ltd.) was mixed.
FEM-450, 450 g/m ² ) was coated so that the glass content was 60% by weight. Both sides were wrapped with polyethylene film, and then the whole was wrapped with cellophane film and aged at 40°C for 24 hours. After ripening,
A sheet molding compound with good peeling from the polyethylene film and no tack was obtained. When this was molded at 140° C. for 3 minutes at a pressure of 80 kg/cm ² , a molded product with a good appearance was obtained. The strength of the molded product was 42 Kg/mm ² in bending strength, 1400 Kg/mm ² in flexural modulus, and 25 Kg/mm ² in tensile strength, showing particularly high tensile strength.

Claims (1)

[Scope of Claims] 1 (A) After reacting 1.0 equivalent of bisphenol epoxy resin or novolac epoxy resin with less than 1.0 equivalent of unsaturated monobasic acid, a polyfunctional alcohol, maleic acid, maleic anhydride and fumaric acid are reacted. A resin composition comprising an unsaturated ester obtained by reacting one or more acids and (B) a polymerizable monomer. 2. The resin composition according to claim 1 or 2, wherein the unsaturated monobasic acid is acrylic acid or methacrylic acid.