JPS58215421A - Production of air-drying unsaturated polyester resin - Google Patents

Abstract

PURPOSE:To obtain an air-drying unsaturated polyester resin improved in adhesion to metals and water resistance, by reacting a tricycloalkane with a polybasic acid, a polyalcohol and a polyalcohol allyl ether. CONSTITUTION:A tricycloalkane of formula I , wherein X is hydroxyl, carboxyl or hydroxyalkyl and n is 0-8, is reacted with a polybasic acid, a polyalcohol and a polyalcohol allyl ether. The tricycloalkanes used are usually those of formulas II, III, IV and V, and these are used alone or as a mixture. When used as a dicarboxylic acid, this tricycloalkane is used in a molar ratio of 0.3-0.6 with respect to the total acid component, and when used as a dihydric alcohol, it is used in a molar ratio of 0.25-0.97 with respect to the total glycol component.

Description

[Detailed description of the invention] The allyl group-containing unsaturated polyester resin obtained by reacting polybasic acid, polyhydric alcohol, and polyhydric alcohol allyl ether can be used as an air-drying paint for general woodworking, and also for automobile repair. (It is useful as a sealing material for joints in buildings, around slats, insets in glass, etc.)

1-Paint 1. Although it has other characteristics such as gloss, texture, and beautiful finish, the present invention further adds adhesion to metal and water resistance to the above performance,
An air-drying unsaturated polynisdelyl ester is produced by reacting tricycloalkanes, polybasic acids, polyhydric alcohols, and polyhydric alcohols represented by 4 (integer, number) from 0 to R. By introducing the above-mentioned tricycloalkanes, air-drying unsaturated polyvarnish 46111
While taking advantage of the inherent characteristics of Fr, the metal adhesion and water resistance have been greatly improved to 11? l1
The liJ silister property is significantly improved.

Tricycloalkanes are fossils represented by the above general formula! ), tricyclodecanes (x-CfD-X) are most advantageously used.

In the above, the position of X is arbitrary or [
x (Kyouyu x ), and these can be used alone or as a mixture.

x is a hydroxyl group, a carboxyl group, a hydroxyalkyl group (
For example, hydroxymethyl group, hydroxyethyl group, etc.).

In producing the unsaturated polyester resin of the present invention using the above tricycloalkanes, polybasic acids, polyhydric alcohols, polyhydric alcohol allyl ethers, and tricycloalkanes may be reacted according to a conventional method. .

Tricycloalkanes are classified into dihydric carboxylic acids and dihydric alcohols depending on the type of X.

Of course, these dihydric carboxylic acids and dihydric alcohols can be used together in the production of unsaturated polyesters1, and when used as an alcohol, the use of other polyhydric alcohols may be omitted, or when used as an acid, other polyhydric alcohols may be omitted. It is also possible to omit the use of polybasic acids.

When used as a dihydric alcohol, the ratio is 0.6 to 0.6 mole based on the total acid content, and when used as a dihydric alcohol, the ratio is 11.25 to 0.97 based on the total glycol content. When used in the range of 3) kernels used in a molar ratio, the 1^+-1- young fruit has particularly remarkable properties such as metal adhesion and water resistance.

An unsaturated acid is used as the polybasic acid, and a saturated acid is used in combination if necessary.

Examples of unsaturated acids include maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, etc., and examples of saturated acids include 11 phthalic anhydride, phthalic acid, terephthalic acid, isophthalic acid, Hett's acid, and adipic acid. , tetrahydrophthalic anhydride, and the like.

In addition, polyhydric alcohols that are degenerate with nucleic acids include:
Ethylene glycol, glopylene glycol, diethylene glycol, triethylene glycol, diethylene glycol, bisphenol dioxyglobyl edel,
Examples include 1.6-butylene glycol, 2.6-butylene glycol, neopentyl glycol, trimethylolpropane, and chrycerin.

Examples of the polyhydric alcohol allyl ether used in polycondensation include pentaerythritol triallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, trimethylolethane diallyl ether, and glycerin diallyl ether. Both are ethers containing at least 111iil hydroxyl groups in the molecule. The content of allyl groups is preferably 0.05 to 2 moles as allyl groups per mole of the acid component, and 0.1 to 1.5 moles is appropriate; if it is less than 0.05 moles, air drying properties are insufficient, Introducing more than a molar amount results in a decrease in blister resistance.

The unsaturated polyester resin of the present invention is mixed with a crosslinkable monomer and used for paints.

As the crosslinkable monomer, any of the known crosslinkable monomers 114C for unsaturated polynisdelic acid can be used, including styrene, vinyltoluene, monochlorostyrene, diallyl phthalate, methyl methacrylate, vinyl acetate, glycidyl methacrylate.

161 additives for other paints and 17-[pigments, fillers,
These include photopolymerization initiators, curing agents, curing accelerators, diluents, thermoplastic resins, etc.

Examples of pigments include titanium white, cyanine blue, chrome yellow, watching red, red iron, carbon black, and aniline black.

Examples of fillers include Vi calcium carbonate, clay, talc, mica, asbeth 1 powder wood, fine powder silica, Varicum sulfate, stearin M curve, lithopone, and the like.

As a curing agent, methyl ethyl ketone peroxide, cyclohexanone peroxide, penzoyl peroxide,
Examples include dicumyl peroxide and tertiary glutyl perbenzoate.

Examples of the curing accelerator include cobalt octenoate, cobalt naphthenate, and manganese naphthenate.

Diluents and [7] ethyl acetate, toluene, xylene, methanol, ethanol, butanol, acetone, MI
BK, Mli: include cellosolve, diacetone alcohol, etc.

Examples of the thermoplastic resin include cellulose acetate zotylate, nitrocellulose, salt vinyl acetate resin, vinyl acetate resin, acrylic resin and copolymers thereof, butylated melamine, butylated urea, and the like.

Other additives include phosphoric acid, tartaric acid, phosphorous acid, oils and fats, silicone oil, surfactants, and paraffin wax.

Next, the method of the present invention will be explained in more detail with reference to examples.Example 1 In a 21 flask equipped with a stirrer and a reflux condenser, 249.5 y of maleic anhydride, 130.4 p of tetrahydro anhydride phthalallyl pentaerythritol, 63y1 of xylene and 0.229% of hydroquinone were charged and the mixture was heated at 150 to 195°C for 6 hours, and after the esterification reaction was carried out for ttΔ at 195°C, xylene was distilled off under reduced pressure at 150°C for 1 hour. Acid value 20 Take 1 loaf of KOH-less polyester and dilute it with styrene to obtain a solid content of 65516 fI 11 degrees 2
jn [ICPS (measured at 2[]°C)].

In addition, as a control example 1, an acid value of 18 KOII "f/y and a viscosity of 1800 CP was prepared in the same manner as in Example 1 except that ethylene glycol was used instead of tricycloalkanes.
S, a paste liquid with a solid content of 67% was obtained 1. This resin liquid was diluted with 1/1 methylene, and further 0.5% of cobalt octenoate (containing 8% cobal) and methyl ethyl ketone peroxide (Parnock) were added. -N, manufactured by NOF), 1. After mixing U%, it was applied to Bonde board-E using a spray gun, and the water resistance and metal closeness of the clear coating film were examined.

Furthermore, the resin liquid 3 of Example-1) and Control Example-1)
20 ytic to “L styrene 6511 talc 546
p, titanium oxide 55y1 cobalt octenoate (f4 containing 896 cobalt) IOy was added and kneaded in a Nigoo to produce a putty for repairing a car. 1.0% was added to a polished mild steel plate, and its water resistance and metal adhesion were examined.

The evaluation method is Tsuruto Spray for 24 hours.

The presence or absence of blisters after 48 hours and 96 hours and the quality of metal adhesion by bending were compared. Furthermore, the adhesion was also compared using the Ericyan test.

Table 1 Examples 2 to 5 The unsaturated polyesters shown in Table 2 were produced according to Example 1.・The ties of seven are shown in Table 2.

Table 2

Claims (1)

[Claims] A method for producing an air-drying unsaturated polyester resin, which comprises reacting tricycloalkanes represented by [an integer of 0 to 8)], a polybasic acid, a polyhydric alcohol, and a polyhydric alcohol allyl ether.