JPS5817111A - Curable resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition. More specifically, it is a curable resin composition that has excellent heat resistance and tack-free properties when used in TARPLEGS and premixes.

Unsaturated alkyd compounds are impregnated into reinforcing materials such as paper, organic fibers, and glass fibers as a composition with crosslinking monomers such as styrene, methacrylate, diallyl phthalate, etc., and molded into prepreg or premix state. Prepreg is used for insulating boards, fishing rods, decorative boards, etc. Premix is used as a molding material for BMC, housing equipment, electrical parts, industrial parts, automobiles, etc.
It is used in a wide variety of applications, including vehicle parts. ``However, for example, in the case of a prepreg for an insulating board, tack-free properties are required in the prepreg state in order to improve manufacturing properties.

To meet this demand, diallyl phthalate,
Diallyl phthalate prepolymer is used in combination with an unsaturated alkyd compound, but diallyl phthalate does not have sufficient tack-free properties, and diallyl 7-thaleate prepolymer! −, the fish will be at a disadvantage due to its salmon-eating property. Furthermore, the molded and cured prepreg product is required to have better heat resistance. For this purpose, special acids of unsaturated alkyd compounds, aromatic or heterocyclic compounds as glycols are used as components, but the solubility and There is an @ field for improving other physical properties. Additionally, the addition of heterocyclic crosslinking agents such as triallyl cyanurate and triallyl isocyanurate improves heat resistance, but since they are liquid, they do not have sufficient tack-free properties and are also expensive. It has drawbacks such as limited use.

The inventors have identified these drawbacks! - We have conducted extensive research into methods for producing prepregs and premixes, which have been improved and have excellent tack-free properties, high heat resistance, and are comparable in price to diallyl phthalate, and have been developed using the general formula The inventors focused on the fact that the polymerizable isocyanuric acid compound used in the manufacturing process has high heat resistance, and is unshapely at room temperature, and completed the present invention with the aim of imparting tack and physical properties to prepregs (premixes). reached.

That is, the present invention contains an unsaturated alkyd compound and an unsaturated compound represented by the general formula (hereinafter referred to as a polymerizable isocyanuric metal oxide), and does not contain any vinyl monomers (V%). The composition is provided in the polyurethane resin composition 1.

The unsaturated alkyd compound used in the present invention is a condensation of a dibasic acid component and a glycol component,
Among these, dibasic acid components include 1, known and commonly used α, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citracone, chlorinated maleic acid, etc.
β-unsaturated dibasic acids, and 7-thalic anhydride, iso-italic acid, terephthalic acid, monochloro-7-thalic acid, Schifferulfthalic acid, triflulphthalic acid, Hett's acid, tetraflulphthalic anhydride, tetraphthalic anhydride, Examples include saturated dibasic acids such as endomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, adipic acid, cepatic acid, cohelic acid, glutaric acid, and pimelic acid, and α, β to unsaturated dibasic acids. As an essential component, scissors α, I-
-mv of the unsaturated dibasic acid may be replaced with the above saturated dibasic acid.

On the other hand, examples of glycol components include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and triethylene! Leecol, 1.3-butylene glycol, 2.5-butylene glycol, 1.4-butylene glycol, neopentyl glycol, hexylene glycol, octylene glycol, bisphenol A1 hydrogenated bisphenol, bisphenol A/dioxy Examples include ethyl ether or dioxyglobyl ether adducts, and alkylene oxides such as ethylene oxide, tetrapyrene oxide, and butylene oxide are also used as glycol components. A polyhydric alcohol can also be used in combination.

The polymerizable isocyanuric acid synthesis is, for example, trimerization of an incyanate group-containing acrylic ester compound obtained by a polyaddition reaction of a hydroxyl group-containing acrylic ester compound and a polyisocyanate compound. Such hydroxyl group-containing acrylic ester compounds include hydroxyethyl (meth)acrylate, human xypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyoctyl (meth)acrylate,
Examples include hydroxybenzyl (meth)acrylate. In addition, as polyisocyanate compounds, tetramethylene diisocyanate (hexamethylene diisocyanate), 1,4-cyclohexane diisocyanate)
, 1.5-cyclohexane diisocyanate, xylylene diisocyanate), 4.4'-diphenylmethane diisocyanate), 2.4-) lylene diisocyanate, 2
．． Known and commonly used diisocyanates such as 6-xylylene diisocyanate and naphthalene diisocyanate, and polyfunctional polyisocyanates such as polymethylene polyphenylene polyisocyanate are used. Such a polyinocyanate compound and the hydroxyl group-containing acrylic ester compound are subjected to a polyaddition reaction so as to leave at least one inocyanate group in the molecule, and then the inocyanate group is added to a quaternary amine II (for example, hydroxybenzyltrimethyl Ammonium χ tertiary amines (
For example, the trimerization reaction is carried out with a catalyst such as trisdimethylaminomethylphenol), and isocyanuric Il! A polymerizable isocyanuric compound is obtained by forming .

Of course, the composition of the present invention can be cured by heating as a mixture of the unsaturated alkyd compound and the polymerizable isoquanur compound as it is, or as a premix.
It is also possible to dissolve the volatile solvent Ki1 and use it for producing prepreg. The above volatile solvents include acetone,
Examples include methanol, ethanol, toluene, ethyl acetate, xylene, benzene, and appropriate mixtures thereof.

In addition, when the composition of the present invention is used for prepregs and premixes, fibrous reinforcing materials include glass roving,
Chopped Strand Mat, Chimiked Continuous Strand Mat, Roving Cloth,
Examples include glass fibers such as glass cloth, longitudinal fibers, poron fibers, metal fibers, general-purpose organic fibers, nonwoven fabrics, woven fabrics, and paper.

Curing of the compositions of the invention is carried out using conventional curing agents such as benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, t-butyl peroxybenzoate. .

Furthermore, the composition of the present invention contains a curing accelerator; a photonic agent such as calcium carbonate, clay, aluminum hydroxide, and glass powder; a mold release agent such as zinc stearate; a pigment; a thermoplastic resin; a curing modifier; Thickening agents such as metal oxides can also be added.

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples. In addition, all examples and percentages are based on weight.

Synthesis Example 1 Synthesis 3 of [monolytic incyanuric acid compound A]
650 g of β-hydroxyethyl methacrylate, 519 rosebenzoquinone a, t-butylcatechol Q, 25II, and 125 g of di-n-butyltin diurate were placed in a glass flask and heated to 50° C. while stirring.

Next, TDI-80 () lylene diisocyanate 2 (manufactured by Mitsubishi Kasei) 87oIIV was added dropwise over about 1 hour,
The reaction temperature was controlled at 80°C. The isocyanate equivalent weight of the reaction product after being held for 1 hour after the completion of the dropwise addition was 566. After cooling the reaction mixture to t-60°C, a 40-methanol solution of penzyltrimethylamyl hydroxide/trimethylhydroxide t5
When I was added, it generated heat to 80°C after about 20 minutes, and
The isocyanate equivalent of the product obtained after holding for a period of time is 2
Ethanol 2I was added to each at 3150°C, and after cooling, the mixture was taken out at 60°C.

The reaction product was yellow in color and solidified when left at room temperature.

Synthesis Example 2 Synthesis of [Polymerizable Isocyanurate Compound B] 3I Into a glass flask, 657 g of β-hydroxypyl methacrylate), non-α65p in rosebenzo, and t
-Butylcatechol α32F and di-n-butyltin chloride α321 were charged and heated to 50° C. while stirring.

Next, 4,4'-diphenylmethane diisocyanate (trade name Isone) 143-L, manufactured by Mitsubishi Kasei ■) 112
5 #v was added dropwise over about 1 hour, and the reaction temperature was maintained at VaO°C.

After the dropwise addition was completed, the isocyanate equivalent was found to be 725 when held for 1 hour. Reactant t - After cooling to 60°C, a 40% methanol solution of benzyltrimethylammonium hydroxide t9. When fv was added, it generated heat to 8-5°C after about 15 minutes. When the reaction mixture was held for an additional 1 hour, the isocyanate equivalent weight of the reaction product was 17,850. 2 g of ethanol was added to this, and after cooling, it was taken out at 60°C. The reaction product was yellow in color and solidified while standing at room temperature.

Examples 1 to 5, Comparative Examples 1 to 3 An unsaturated alkyd containing 2 moles of propylene glycol, 91 moles of phthalate, and 11 moles of maleic acid polycondensed by a conventional method was added to a heating device equipped with a heating device together with a fragility monomer in the proportions shown in Table 1. The mixture was added to a Nigu and thoroughly mixed and stirred. Next, 100 parts of calcium carbonate, 5 parts of zinc stearate, and 15 parts of dicumyl peroxinide as a hardening agent were kneaded in order and thoroughly mixed and stirred. 111 parts and 20 parts were kneaded into a 4-inch glass chopped strand 1. A tux molding material was obtained in a puri and cooled at room temperature.

A predetermined amount of these molding materials was put into a metal 11 heated to 160° C., and pressure molding '1 was carried out for 4 minutes to obtain a molded plate having a thickness of 3 cm.

These physical property values are shown in Table-1.

Examples 4-5, Comparative Examples 4-5 The unsaturated alkyd obtained by polycondensing 2 moles of propylene glycol, 1 mole of isophthalic acid and 1 mole of malein WR by a conventional method and each crosslinking monomer are as shown in Table 2. The mixture was blended, dissolved at 120 to 130°C, and further diluted with a mixed solvent of methyl ethyl ketone and toluene. To 100 parts of this resin solution, 3 parts of zinc stearate and 1 part of t-butylhachenzoate were mixed and stirred, and the mixture was impregnated into Glass PS so that the reinforcing material content was 40%.
The solvent was evaporated at ~50°C for 2 hours to obtain a prepreg.

These prepregs were heat-molded in a hot plate at a temperature of 140° C. for 4 minutes to obtain a flat plate with a thickness of 2 cm. These physical property values are shown in Table-2.

It should be noted that molded articles made from the composition of the present invention have a patented property that they have high surface hardness, are resistant to scratches from scratches, and have good adhesion when painted.

Claims (1)

[Claims] Unsaturated alkyd compounds and general formula (B: alkylene, phenylene and derivatives thereof B': C
A curable resin composition containing an unsaturated compound represented by 2-C3 alkylene B": hydrogen and C1-C4 alkyl) and containing no other vinyl monomer.