JPH0150326B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermosetting epoxy acrylate resin compositions. The thermosetting epoxy acrylate resin composition herein refers to a resin composition in which the epoxy acrylate resin produced in the present invention is mixed with a liquid polymerizable monomer, and its purpose is to reduce viscosity change over time. An object of the present invention is to provide a thermosetting epoxy acrylate resin composition which has a small viscosity and has excellent thickening properties in the presence of alkaline earth metal oxides or hydroxides. Conventionally, thermosetting epoxy acrylate resin compositions made by mixing reaction products of epoxy resins with α,β-unsaturated monobasic acids and liquid polymerizable monomers such as styrene monomers have excellent corrosion resistance. Because of its strength and toughness, it has been widely used as a matrix for various reinforced plastics. In particular, it is expected to be used as a structural material that takes advantage of its toughness, such as in automobile parts. However, in order to expand these applications, it is essential to improve productivity. reinforcing agent, hardening agent,
A molding compound called SMC (abbreviation for sheet molding compound) or BMC (abbreviation for bulk molding compound) is created by blending mold release agents, polymerization inhibitors, fillers, thermoplastic resins, colorants, etc. It must be made into a material and then manufactured into a product using a molding method such as compression molding, transfer molding, or injection molding. In particular, when producing SMC, the epoxy acrylate resin composition must be thickened so that the protective film covering the SMC product can be easily peeled off during molding of the SMC. However, since there is no carboxyl group in the main chain of the reaction product obtained by reacting an epoxy resin with an α,β-unsaturated monobasic acid, the epoxy acrylate resin composition obtained using this reaction product When the product is made into SMC, it has not been possible to thicken it using thickeners such as alkaline earth metal oxides or their hydroxides. In order to eliminate such inconveniences, U.S. Patent No. 3,466,259 discloses that epoxy resin and α, β
- Thickening with a thickener by reacting a polybasic acid anhydride with a secondary hydroxyl group present in the reaction product obtained by reacting with an unsaturated monobasic acid and introducing a carboxyl group. Technologies have been proposed to realize this. However, when the epoxy acrylate resin composition obtained by this method is left at room temperature, the viscosity increases over time and has poor storage stability, which is not only inconvenient in terms of product quality control, but also requires process control during SMC manufacturing. This is inconvenient and ultimately makes it impossible to manufacture molded products with stable quality. The inventors of the present invention have focused on the above-mentioned disadvantages and have conducted various studies in order to solve the above-mentioned disadvantages, and as a result, have arrived at the present invention. The present invention provides a reaction product a having a secondary hydroxyl group obtained by reacting (A) an epoxy compound having at least one epoxy group in the molecule with an α,β-unsaturated monobasic acid. per equivalent of secondary hydroxyl group
An amount of 0.1 to 1.0 mol of polybasic acid anhydride b is reacted, and then 0.02 to 1 mol of said polybasic acid anhydride b is reacted.
30 to 80 parts by weight of an epoxy acrylate resin obtained by reacting ~1.0 mol of acrylic acid or methacrylic acid ester c having at least one alcoholic hydroxyl group in the molecule and (B) liquid polymerizable monomer 20 to 70 parts by weight of a thermosetting epoxy acrylate resin composition, in particular, after reacting with a polybasic acid anhydride as described above, then acrylic acid or methacrylic acid having an alcoholic hydroxyl group. The feature is that the desired epoxy acrylate resin is obtained by reacting esters. The epoxy acrylate resin composition of the present invention obtained in this way shows extremely little change in viscosity over time, and in addition, an excellent thickening effect is achieved by the thickener, that is, the oxide or hydroxide of an alkaline earth metal. In terms of quality control,
The present invention provides an epoxy acrylate resin composition that presents no problems in SMC manufacturing process control and is suitable for practical use. The epoxy compound used in the present invention refers to a compound having at least one epoxy group in one molecule, and usually has an epoxy equivalent of 100
~4000, preferably 130-1000 epoxy resin. Specifically, for example, epichlorohydrin,
Examples include condensates of epihalohydrins such as methylepichlorohydrin and bisphenol compounds or novolaks. Here, examples of bisphenol compounds include 2,2-bis(4
-Hydroxyphenyl)propane (bisphenol A), halogenated bisphenol A, 2,2-
Bis(4-hydroxyphenyl)methane (bisphenol F) is a typical example, and novolaks are produced by reacting phenolic compounds such as resorcinol, tetrahydroxydiphenylmethane, phenol, or cresol with formaldehyde. The resulting condensates are exemplified. Other examples of the epoxy resin include diglycidyl ether compounds obtained by reacting diols with epichlorohydrin or methyl epichlorohydrin, and tetraglycidyl ether of tetraphenylethane.
These epoxy compounds can be used alone or in combination of two or more. Examples of the α,β-unsaturated monobasic acid to be reacted with the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, and sorbic acid, and two or more of these may be used in combination. Furthermore, if desired, a saturated monobasic acid or a saturated polybasic acid may be used in combination. The polybasic acid anhydride b to be reacted with the reaction product a obtained by reacting an epoxy compound and an α,β-unsaturated monobasic acid includes maleic anhydride, citraconic anhydride, itaconic anhydride, and phthalic anhydride. ,
Tetrahydrophthalic anhydride, 3,6-endomethylene-1,2,3,6-tetrahydro-cis-phthalic anhydride, methyltetrahydrophthalic anhydride,
Examples include methylnadic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, trimellitic anhydride, etc., and two or more of these may be used in combination as desired. Next, acrylic acid or methacrylic acid ester c having at least one alcoholic hydroxyl group in the molecule is added to the resulting reaction product and reacted [In the following description, acrylic acid or methacrylic acid is referred to as (meth)acrylic acid. Note, (meta)
Similar notations apply to related compounds such as acrylates. ] as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane mono(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol Examples include di(meth)acrylate, pentaerythritol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, which may be used alone or in combination of two or more. can be used. The epoxy compound and the α,β-unsaturated monobasic acid are reacted at an equivalent ratio of epoxy group to carboxyl group of 1:0.8 to 1.2, and other conditions such as reaction temperature are set under known conditions. All you have to do is hire
For example, the reaction is carried out at a temperature of 80 to 150°C in the presence of an esterification catalyst. As the esterification catalyst used here, known compounds can be used, such as secondary amines, tertiary amines, inorganic or organic acid salts of these amines, metal phthalates, metal halides, etc. can be mentioned. The reaction product a thus obtained always has a pendant secondary hydroxyl group in the molecule, and the addition reaction of the polybasic acid anhydride b to the secondary hydroxyl group requires the addition of this hydroxyl group. for 1 equivalent
A polybasic acid anhydride is used in an amount ranging from 0.1 to 1.0 mol, and the reaction is allowed to proceed until the addition rate of the used polybasic acid anhydride to hydroxyl groups reaches 60 to 90%.
Then, the reaction product obtained has at least one alcoholic hydroxyl group in the molecule in an amount ranging from 0.02 to 1.0 mol per mol of anhydride b based on the amount of polybasic acid anhydride b used previously. (meta)
(meth)acrylic ester c is added to the extent that the amount of polybasic acid anhydride remaining in the reaction product is 30% or less, preferably 10% or less of the amount initially used. Carry out reaction c. The reaction involving polybasic acid anhydride b is 50
It may be carried out at a temperature in the range of ~150°C. When producing epoxy acrylate resin according to the above recipe, phenols, quinones, metallic copper, copper salts, etc. are used for the purpose of preventing gelation, imparting preservability, or adjusting hardenability. It is effective to use a polymerization inhibitor if necessary. In this way, the desired epoxy acrylate resin A is obtained. This epoxy acrylate resin A is
Liquid polymerizable monomer B, such as styrene, vinyltoluene, p-methylstyrene, divinylbenzene, chlorostyrene, α-methylstyrene, t-
Butylstyrene, diallyl phthalate, (meth)
The epoxy acrylate resin composition of the present invention is obtained by mixing with one or more lower alkyl esters of acrylic acid. This composition can be used as a thermosetting epoxy acrylate resin composition with little change in viscosity over time. If the step of reacting the unreacted dibasic acid anhydride in the reaction product with a (meth)acrylic ester having at least one alcoholic hydroxyl group in the molecule is omitted, the resulting epoxy acrylate resin and liquid The epoxy acrylate resin composition formed by mixing with a polymerizable monomer increases in viscosity over time,
A compound with stable viscosity cannot be obtained, and as a result, a molded product with stable quality cannot be obtained. Therefore, the above reaction step in the present invention is extremely important. The thermosetting epoxy acrylate resin composition obtained by the present invention has a thickener such as an oxide of an alkaline earth metal such as magnesium oxide, magnesium hydroxide, calcium oxide, or calcium hydroxide or a hydroxide thereof. In addition, fillers such as calcium carbonate, calcium sulfate, and aluminum hydroxide; t-butyl perbenzoate,
It is compounded by blending various additives such as a polymerization initiator such as benzoyl peroxide; a mold release agent such as zinc stearate and calcium stearate. Thermoplastic resin, colorant, polymerization inhibitor, fiber reinforcing agent, etc. are added to this compound as necessary to obtain molding materials such as SMC and BMC with stable quality. The thermosetting epoxy acrylate resin composition of the present invention comprises a polymerization initiator such as cyclohexanone peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, cumene hydroperoxide, cobalt naphthenate, cobalt octenoate,
By using it in appropriate combination with a curing accelerator such as manganese naphthenate or dimethylaniline, it can also be used as a curable resin material suitable for curing at room or medium temperatures. The present invention will be specifically explained below using Examples. Synthesis Example 1 "Epicote 828" [trade name, epoxy resin manufactured by Yuka Ciel Epoxy Co., Ltd., epoxy equivalent weight 191] 2292 was placed in 5 reactors equipped with a stirrer, thermometer, and cooler.
g, methacrylic acid 1032g, styrene monomer 1428g
g, triethylamine 6.7 g, and toluhydroquinone 1.3 g were charged, the temperature was raised to 120° C., and the reaction was carried out for 3.5 hours to obtain an epoxy acrylate resin (1) having an acid value of 5.0 mg KOH/g. Synthesis Example 2 "Epicote 1001" in the same reactor as Synthesis Example 1
[Product name: Epoxy resin manufactured by Yuka Ciel Epoxy Co., Ltd.]
Epoxy equivalent 484〕1927g, methacrylic acid 320g,
Styrene monomer 1502g, triethylamine 4.5g
g and 1.8 g of toluhydroquinone, and heated to 120℃.
The temperature was raised to 130°C for 2 hours, and then the temperature was raised to 130°C and the reaction was carried out for 1 hour to give an acid value of 4.5 mg.
An epoxy acrylate resin (2) containing KOH/g was obtained. Synthesis Example 3 "Epicote 1001" in the same reactor as Synthesis Example 1
[Epoxy equivalent 472] 2075g, acrylic acid 288g,
Styrene monomer 1580g, triethylamine 4.7
g and 1.9 g of toluhydroquinone, 120
The temperature was raised to ℃ and reacted for 3 hours, and the acid value was 5.3 mgKOH/
g of epoxy acrylate resin (3) was obtained. Example 1 Epoxy acrylate resin (1) obtained in Synthesis Example 1 was placed in a 7-reactor equipped with a stirrer, thermometer, and cooler.
4760 g, maleic anhydride 352 g, and styrene monomer 151 g were charged and reacted at 100°C for 1 hour to produce epoxy acrylate resin a with an acid value of 41.2 mgKOH/g (total acid value 45.8 mgKOH/g) and a viscosity of 550 centipoise (25°C). Obtained. The reaction rate of maleic anhydride is 88
It was %. 260g of 2-hydroxypropyl methacrylate was added to the obtained resin a, and the temperature was further heated to 100°C.
The mixture was reacted for 4 hours to obtain a desired thermosetting epoxy acrylate resin composition A having an acid value of 38.0 mgKOH/g (total acid value of 38.8 mgKOH/g) and a viscosity of 570 centipoise (25°C). Example 2 Into the same reactor as in Example 1, 4,760 g of the epoxy acrylate resin (1) obtained in Synthesis Example 1, 692 g of trimellitic anhydride, and 1,254 g of styrene monomer were charged.
Acid value 64.6mgKOH/g after reacting at 100℃ for 1.5 hours
(Total acid value 69.1 mgKOH/g) and viscosity 820 centipoise (25° C.) Epoxy acrylate resin b was obtained.
The reaction rate of trimellitic anhydride was 85%. 116 g of 2-hydroxyethyl acrylate was added to the obtained resin b and further reacted at 100°C for 3 hours to obtain an acid value of 63.0 mgKOH/g (total acid value 64.0 mgKOH/g),
A target thermosetting epoxy acrylate resin composition B having a viscosity of 830 centipoise (25° C.) was obtained. Example 3 In the same reactor as in Example 1, 3755 g of epoxy acrylate resin (2) obtained in Synthesis Example 2 and maleic anhydride were added.
Prepared 219g and 146g of styrene monomer, 100g
The reaction was carried out at ℃ for 1 hour to obtain epoxy acrylate resin c having an acid value of 42.9 mgKOH/g (total acid value of 46.9 mgKOH/g) and a viscosity of 1270 centipoise (at 25℃).
The reaction rate of maleic anhydride was 87%. 133 g of pentaerythritol triacrylate was added to the obtained resin c, and the reaction was further carried out at 100°C for 3 hours, resulting in an acid value of 40.3 mg KOH/g (total acid value of 40.8 mg).
A target thermosetting epoxy acrylate resin composition C having a viscosity of 1340 centipoise (25° C.) and a viscosity of 1340 centipoise (25° C.) was obtained. Example 4 Into the same reactor as Example 1, 3755 g of epoxy acrylate resin (2) obtained in Synthesis Example 2 and 494 g of phthalic anhydride were added.
g and 329 g of styrene monomer were charged and reacted at 100°C for 3 hours to obtain an acid value of 45.2 mgKOH/g (total acid value 55.8 mgKOH/g) and a viscosity of 1290 centipoise (25
An epoxy acrylate resin d (°C) was obtained. The reaction rate of phthalic anhydride was 74%. 229 g of 2-hydroxyethyl methacrylate was added to the obtained resin d, and the reaction was further carried out at 100°C for 4 hours, resulting in an acid value of 41.5 mg KOH/g (total acid value of 45.8 mg).
A target thermosetting epoxy acrylate resin composition D having a viscosity of 1100 centipoise (25° C.) and a viscosity of 1100 centipoise (25° C.) was obtained. Example 5 Into the same reactor as in Example 1, 3755 g of the epoxy acrylate resin (2) obtained in Synthesis Example 2, 214 g of trimellitic anhydride, and 143 g of styrene monomer were charged.
Reacted at 100℃ for 1 hour, acid value 35.9mgKOH/g
An epoxy acrylate resin e having a total acid value of 37.9 mgKOH/g and a viscosity of 4020 centipoise (25°C) was obtained. The reaction rate of trimellitic anhydride was 87%. 76 g of 2-hydroxypropyl acrylate was added to the obtained resin e, and the reaction was further carried out at 100°C for 3 hours, resulting in an acid value of 33.0 mgKOH/g (total acid value of 33.4 mg).
A target thermosetting epoxy acrylate resin composition E having a viscosity of 4100 centipoise (25° C.) and a viscosity of 4100 centipoise (25° C.) was obtained. Example 6 In the same reactor as Example 1, 3949 g of epoxy acrylate resin (3) obtained in Synthesis Example 3 and 474 g of phthalic anhydride were added.
g and 315 g of styrene monomer were charged and reacted at 100°C for 3 hours to obtain an acid value of 38.9 mgKOH/g (total acid value 47.6 mgKOH/g) and a viscosity of 1010 centipoise (25
℃) epoxy acrylate resin f was obtained. The reaction rate of phthalic anhydride was 77%. 175 g of 2-hydroxyethyl methacrylate was added to the obtained resin f, and the reaction was further carried out at 100°C for 4 hours, resulting in an acid value of 36.3 mg KOH/g (total acid value of 39.7 mg).
A target thermosetting epoxy acrylate resin composition F having a viscosity of 980 centipoise (25° C.) and a viscosity of 980 centipoise (25° C.) was obtained. Example 7 Each of the epoxy acrylate resin compositions A to F and a to f obtained in Examples 1 to 6 was left in a constant temperature room at 40°C, and the stability of the viscosity over time was examined. The results are shown in Table 1. As is clear from the results in Table 1, the viscosity of thermosetting epoxy acrylate resin compositions A to F of the present invention treated with (meth)acrylic ester having an alcoholic hydroxyl group shows excellent stability over time. I understand that. Table 2 shows the thickening properties of compounds using thermosetting epoxy acrylate resin compositions A to F of the present invention. The composition of the compound is as follows. Resin composition 100 parts (weight) Calcium carbonate 100 parts Zinc stearate 3 parts Magnesium oxide 2 parts [manufactured by Kyowa Kagaku Kogyo Co., Ltd., product name "Kiyowa Mag"]
100''] However, since the resin composition E of Example 5 had a high viscosity, the following compound composition was adopted. Resin composition E 90 parts (weight) Styrene monomer 10 parts Calcium carbonate 100 parts Zinc stearate 3 parts Magnesium oxide 2 parts [manufactured by Kyowa Kagaku Kogyo Co., Ltd., product name "Kiyowa Mag"]
100''] As is clear from the results in Table 2, the thermosetting epoxy acrylate resin composition of the present invention exhibited good thickening properties.

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Claims (1)

[Claims] 1 (A) A reaction product a having a secondary hydroxyl group obtained by reacting an epoxy compound having at least one epoxy group in the molecule with an α,β-unsaturated monobasic acid, Polybasic acid anhydride b in an amount of 0.1 to 1.0 mol per equivalent is reacted, and then
30 to 80 parts by weight of an epoxy acrylate resin obtained by reacting acrylic acid or methacrylic acid ester c having at least one alcoholic hydroxyl group in the molecule in an amount of 0.02 to 1.0 mol per mol of the polybasic acid anhydride b; (B) Liquid polymerizable monomer 20~
70 parts by weight of a thermosetting epoxy acrylate resin composition.