JPS5936118A - Thermosetting epoxy acrylate resin composition - Google Patents

Abstract

PURPOSE:To provide titled composition of small variation in viscosity having high thickening performance in the presence of alkaline earth metal (hydr)oxide comprising a liquid polymerizable monomer and epoxy acrylate resin produced by a specific process. CONSTITUTION:The objective composition comprising (A) 30-80pts.wt. of an epoxy acrylate reisn and (B) 20-70pts.wt. of a liquid polymerizable monomer (e.g., 2-hydroxyethyl acrylate). The manufacturing process of the component (A) is as follows: a secondary hydroxyl group-contg. reaction product prepared by the reaction between (1) an epoxy compound having in one molecule at least one epoxy group and (2) an alpha,beta-unsaturated monobasic acid is made to react with 0.1-1.0mol per equivalent of said secondary hydroxyl group of a polybasic acid anhydride followed by reaction with 0.02-1.0mol per mol of the above polybasic acid anhydride, of a (meth)acrylic ester having in one molecule, at least one alcoholic OH.

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 7 acrylate resin produced in the present invention is mixed with a liquid polymerizable monomer, and its purpose is to reduce the viscosity over time. Changes are small;
Another object of the present invention is to provide a thermosetting epoxy 7-acrylate resin composition that exhibits thickening properties in the presence of alkaline earth metal oxides or hydroxides.

Conventionally, thermosetting epoxy acrylate resin compositions made by mixing epoxy resins, α, β-unsaturated acid-base acid reaction products, 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 with strong toughness, such as in automobile parts. However, in order to expand these uses, it is essential to improve productivity, and in order to achieve this purpose, a thermosetting epoxy acrylate resin composition is used as a matrix.
SM is formulated with thickeners, fiber reinforcing agents, curing agents, mold release agents, polymerization inhibitors, fillers, thermoplastic resins, colorants, etc.
It is made into a molding compound called C (abbreviation for Sheet Molding Compound) or BMC (abbreviation for Bulk Molding Compound), and it is made into a product using molding methods such as compression molding, transfer molding, and injection molding. Must be.

In particular, when producing KSMC, 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 acid-base, the epoxy acrylate resin obtained using this reaction product When the composition 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 inconvenience, U.S. Patent Nos. 3 and 4
No. 66.259 discloses that a polybasic acid anhydride is reacted with a secondary hydroxyl group present in a reaction product obtained by reacting an epoxy resin with an α,β-unsaturated acid-base; A technique has been proposed that achieves thickening using a thickener by introducing a carboxyl group. 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 not only causes inconvenience in product quality control, but also makes it difficult to process during SMC production. This is inconvenient in terms of management, and ultimately makes it impossible to manufacture molded products with stable quality.

The inventors of the present invention focused on the above-mentioned lower joint pressure and conducted various studies to solve this problem, and as a result, they arrived at the present invention.

The present invention provides (2) at least one epoxy group in the molecule.
0.1 to 1.0 mol per 1 mol of secondary hydroxyl group (color) is a reaction product with a secondary hydroxyl group that is fl Nosu's polybasic acid anhydride (b) is reacted, and then, at least one molecule is added in an amount of 0.02 to 1.0 mol per 1 mol of the polybasic acid anhydride (b). Acrylic acid or methacrylic acid ester (C) having alcoholic hydroxyl group
Epoxy acrylate resin obtained by reacting 6
0-80 Ichirobe and (B) Liquid polymerizable unit 20-
70 parts by weight of a thermosetting epoxy acrylate resin composition, in particular, after reacting with a polybasic acid anhydride as described above, the composition is then reacted with an acrylic acid or methacrylic ester having an alcoholic hydroxyl group. The process is characterized by the ability to react to obtain the desired epoxy acrylate resin. 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. Therefore, there is no problem in terms of quality control or SMC manufacturing process control, and it provides a practically suitable epoxy acrylate resin and fI composition.

The epoxy compound used in the present invention refers to a compound having at least one epoxy group in one molecule, and usually refers to an epoxy resin having an epoxy molecular weight of 100 to 4000, preferably 130 to 1000. Specific examples include condensates of epihalohydrins such as epichlorohydrin and methylepichlorohydrin and bisphenol compounds or novolacs. Examples of bisphenol compounds include 2,2-bis(4-hydroxyphenyl)furopane (bisphenol A), halogenated bisphenol A, and 2,2-bis(4-hydroxyphenyl)furopane (bisphenol A).
-Hydroxyphenyl)methane (bisphenol F) is a representative example, and novolacs include resorcinol, tetrahydroxydiphenylenemethane, a condensate obtained by reacting a phenolic compound such as phenol or cresol with formaldehyde. is exemplified. Other examples of the epoxy resin include:
Diglycidyl ether compounds obtained by the reaction of diols with epichlorohydrin or methylepichlorohydrin and tetraglycidyl ether of tetraphenylethane can also be mentioned. These epoxy compounds can be used alone or in combination of two or more.

Examples of the α,β-unsaturated unsaturated acid-base acid to be reacted with the above-mentioned epoxy compound include acrylic acid, methacrylic acid, crotonic acid, sorbic acid, etc., and two or more of these may be used in combination; may be used in combination with a saturated basic acid or a saturated polybasic acid, if desired.

The polybasic acid anhydride (b) to be reacted with the reaction product (a) obtained by reacting the epoxy compound with the (X, β-unsaturated base acid) is maleic anhydride, citraconic anhydride, itan anhydride. Acid, hydrothermal phthalic acid, tetrahydrophthalic anhydride, 5,6-endomethylene-1,2,3,6
-Titrahydrosis - Examples include phthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, trimellitic anhydride, etc., and two or more of these can be used as desired. may be used together.

Then, 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 (meth)
It is written as acrylic acid, and related compounds such as (meth)acrylate follow the same notation. 2-hydroxyethyl meth)acrylate, 2-hydroxypropyl (meth)acrylate, trimethylolbroban di(meth)acrylate, trimethylolpropane mono(
Examples include meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. These can be used alone or in combination of two or more.

The epoxy compound and α, β-unsaturated unsaturated acid-base acid 1
The equivalent ratio of epoxy group to carboxyl group is 110.8~
The reaction is carried out at a ratio of 1.2 to 1.2, and the reaction temperature and other conditions may be any known conditions. 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, salts of inorganic or organic acids of these amines, metal phthalates, metal salts, etc. Chemicals, 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 this secondary hydroxyl group uses a polybasic acid anhydride in an amount ranging from 0.1 to 1.0 mol per equivalent of this hydroxyl group, and the addition rate of the used polybasic acid anhydride to the hydroxyl group is 60 to 90%. Let the reaction proceed until the Next, the obtained reaction product is added with molecules in an amount ranging from 0.02 to 1.0 mol per 1 mol of anhydride (b) based on the amount of polybasic acid anhydride (b) used previously. The polybasic acid anhydride having at least one alcoholic hydroxyl group therein (after adding the metacoacrylic acid ester (C), the polybasic acid anhydride remaining in the reaction product is not more than 30% of the amount initially used, preferably 10 The reaction of (meth)acrylic acid ester (C) is carried out to the extent that the concentration is 50 to 1%.The reaction involving the polybasic acid anhydride (b) is
It may be carried out at a temperature in the range of 50°C.

When producing epoxy acrylate resin according to the above recipe, phenols, quinones, metallic copper,
It is effective to use a polymerization inhibitor such as a copper salt, if necessary.

In this way, the desired epoxy acrylate resin (A) is obtained. This epoxy acrylate resin (A) is a liquid polymerizable monomer (B), such as styrene, vinyl citrenine, p-methylstyrene, divinylbenzene, chlorostyrene, α-methylstyrene, t-butylstyrene,
The epoxy acrylate resin composition of the present invention is obtained by mixing with one or more of diallyl phthalate and lower alkyl ester of (meth)acrylic acid.

This composition exhibits little change in viscosity over time (and can be used as a thermosetting epoxy acrylate resin composition. 7 Having a lefuric hydroxyl group (
If the step of reacting with meth)acrylic acid ester is omitted, the epoxy acrylate resin composition obtained by mixing the epoxy acrylate resin and the liquid polymerizable monomer will increase in viscosity over time, and the viscosity will become unstable. A solid compound 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 according to the present invention 1 contains a thickener such as an alkaline earth metal oxide or hydroxide thereof such as magnesium oxide, magnesium hydroxide, calcium oxide, or calcium hydroxide. The viscosity is suitably thickened with calcium carbonate, calcium sulfate,
It is compounded by blending various additives such as a filler such as aluminum hydroxide; a polymerization initiator such as t-butyl perbenzoate and benzoyl peroxide; and a mold release agent such as zinc stearate and calcium stearate. This compound is blended with thermoplastic resin, colorant, polymerization inhibitor, fiber reinforcing agent, etc. as necessary to produce SMC with stable quality.

A molding material such as BMC is obtained.

The thermosetting epoxy acrylate resin composition of the present invention includes:
Intermediate initiators such as cyclohexanone peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, cumene hydroperoxide and cobalt naphthenate,
By using an appropriate combination of a curing accelerator such as cobalt octenoate, 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 In a 5-tub reactor equipped with a stirrer, a thermometer and a cooler, 2292 g of "Ebiko" 828J (trade name, epoxy resin manufactured by Yuka Shell Epoxy ■, epoxy equivalent: 191), 1052 g of methacrylic acid were added.

Styrene monomer 1428g, ) ethylamine 6.7
g and 71.5 g of toluhydrukino, and heated to 120℃.
Raised the temperature to 5.5 hours and reacted for 5.5 hours, acid value 5, O~KO
An epoxy acrylate resin (1) of H/g was obtained.

Synthesis Example 2 In the same reactor as Synthesis Example 1, [Ebiko] 100IJ (product name, epoxy resin manufactured by Yuka Shell Epoxy ■, epoxy equivalent weight 484) 1927g, methacrylic acid 520g1, styrene monomer 1502g,) ethylamine 4,5
Prepare g and 1.8 g of toluhydroquinone, 12
The temperature was raised to 0°C for 2 hours, then the temperature was raised to 150°C and reacted for 1 hour at that temperature, resulting in an acid value of 4.5 to KOH.
/g of epoxy acrylate resin (2) was obtained.

Synthesis example 5 In the same reactor as Synthesis Example 1, "Epifuto io" was added.

1" [epoxy 11:472] 2075g, 79 lyric acid 288g, styrene monomer 1580g1 triethylamine 4.7g and toluhydroquinone
1.9 g was charged, heated to 120° C., and reacted for 5 hours to obtain an epoxy acrylate resin (6) with an acid value of 5.5 #KOH/g.

Example 1 7! equipped with stirrer, thermometer and cooler. The epoxy acrylate resin obtained in Synthesis Example 1 (114,760 g) was placed in the reactor.
, maleic anhydride 552g and styrene monomer 1
51g was prepared and reacted at 100℃ for 1 hour to obtain an acid value of 41.
．． 21RgKOH/g (total acid value 45, 8In9K
An epoxy acrylate resin (at) with a viscosity of 550 centipoise (25°C) was obtained. The reaction rate of maleic anhydride was 8896. 260 g of 2-hydroxypropyl methacrylate was added to the obtained resin (al). Further, the reaction was carried out for 4 hours at i o o ”c, and the acid value was 58°0 KOH/g (total acid value 58.8 KOH/g).
g), and a desired thermosetting epoxy acrylate resin composition (A) having a viscosity of 570 centipoise (25°C) was obtained.

Example 2 4760 g of epoxy acrylate resin f11 obtained in Synthesis Example 1 and trimellitic anhydride were placed in the same reactor as Example 1.
Charge 692g and 1254g of styrene monomer,
Epoxy acrylate resin (b) for 1.5 hours at 00℃
I got l. The reaction rate of trimellitic anhydride was 85%. 116 g of 2-hydroxyethyl acrylate was added to the resulting resin (bl), and the mixture was further reacted at 100°C for 6 hours to give a cete acid value (55,01n9KOH/g (total acid value 6).
4.0■KOH/g), viscosity 850 centipoise (
A desired thermosetting epoxy acrylate resin composition CB) was obtained.

Example 5 Into the same reactor as Example 1, the epoxy acrylate resin obtained in Synthesis Example 2 (215,755 g 1 maic anhydride 219
g and 146 g of styrene monomer and heated to 100°C.
The acid value was 42.9 da KO) L/g (
Epoxy acrylate resin (C
) obtained. The reaction rate of maleic anhydride was 8796.

156 g of pentaerythritol triacrylate was added to the obtained resin (Cl, and the reaction was further carried out at 100°C for 5 hours to give an acid value of 40.5 da KOH/g (total acid value of 40.8
KOH/g), viscosity 1540 centipoise (25
A desired thermosetting epoxy acrylate resin composition (C) was obtained.

Example 4 The epoxy acrylate resin obtained in Synthesis Example 2 (215,755 g, 494 g of phthalic anhydride) was placed in the same reactor as Example 1.
and 529 g of styrene monomer were charged and reacted at 100°C for 5 hours to give an acid value of 45.2 ■KOH/g (total acid value 55.8 ■KOH/g) and a viscosity of 1290 Cef'F-Ho7X (at 25°C). An epoxy acrylate resin fdl was obtained.

The reaction rate of phthalic anhydride was 74%.

229 g of 2-hydroxyethyl methacrylate was added to the obtained resin (dl) and further reacted at 100°C for 4 hours to give an acid value of 41.5 to KOf-1/g (total acid value of 45.
8~KOH/g), viscosity 1100 centipoise (2
A desired thermosetting epoxy acrylate resin composition (D) was obtained.

Example 5 The epoxy acrylate resin obtained in Synthesis Example 2 (215,755 g, trimellitic anhydride) was placed in the same reactor as Example 1.
Charge 214g and 145g of styrene monomer,
React at 0°C for 1 hour, acid value 55.9~KOH/g
(Total acid value 57.9 ■KOH/g), viscosity 402
An epoxy acrylate resin (EL) of 0 centipoise (25°C) was obtained.

The reaction rate of trimellitic anhydride was 87%.

76 g of 2-hydroxypropyl acrylate was added to the resulting resin tel, and the reaction was further carried out at 100°C for 6 hours to give an acid value of 55.0 ■KOH/g (total acid value 55.4 daKOH/g) and a viscosity of 4100 centipoise. (25
A desired thermosetting epoxy acrylate resin composition (E) was obtained.

Example 6 Into the same reactor as Example 1, 474 g of epoxy acrylate resin (515,949 g, anhydrous) obtained in Synthesis Example 5 and p-phosphoric acid were added.
and 515 g of styrene monomer were charged and reacted at 100°C for 5 hours to form an epoxy acrylate resin +f+ with an acid value of 58.9 da KOH/g (total acid value 47.6 KOH/g) and a viscosity of 1010 centipoise (at 25°C).
I got it.

The reaction rate of phthalic anhydride was 77%.

175 g of 2-hydroxyethyl methacrylate was added to the obtained resin Tfl, and the reaction was further carried out at 100°C for 4 hours to give an acid value of 56.5 M9KOH/g (total acid value of 59.7
■KOH/g), viscosity 980 se/Ciboaz (25
A desired thermosetting epoxy acrylate resin composition (F) was obtained.

Example 7 Each of the epoxy acrylate resin compositions A-F and a-f obtained in Examples 1 to 6 was left in a constant temperature room at 40° C., and the stability of viscosity over time was examined. The results are shown in Table 1.

As is clear from the results in Table 1, the viscosity of the thermosetting epoxy acrylate resin compositions A-F of the present invention treated with a (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-F of the present invention.

The composition of the compound is as follows.

Resin composition 100 parts (heavy M) Calcium carbonate 100 parts Zinc stearate 5 parts Magnesium oxide 2 parts [manufactured by Kyowa Chemical Industry ■, trade name [KIYOWA MAG 100J] However, since resin composition E of Example 5 has a high viscosity, , we adopted the following Punbound composition.

Resin composition (E) 90 parts (weight) Styrene monomer 10 parts Calcium carbonate 100 parts Zinc stearate 6 parts Magnesium oxide 2 parts [manufactured by Kyowa Chemical Industry ■, trade name [Kiyowa Mag 100J] As is clear from the results in Table 2 , the thermosetting epoxy acrylate resin composition of the present invention exhibited good thickening properties.

Table 1 Change in viscosity of epoxy acrylate resin composition when left in a constant temperature room at 40°C---

Claims (1)

[Claims] (2) The 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 Polybasic acid anhydride (b) in an amount of 0.1 to 1.0 mol per 1 equivalent of hydroxyl group is reacted, and then 0.02 to 1.0 mol of polybasic acid anhydride (b) is reacted per 1 mol of polybasic acid anhydride (b). Epoxy acrylate resin which can be produced by reacting acrylic acid and methacrylic acid ester (C) having at least one alcoholic hydroxyl group in the molecule of 30 to 80 parts and a polymerizable monomer of 20 to 80 parts 70 parts by weight of a thermosetting epoxy acrylate resin composition.