JPS59179669A - Air-drying unsaturated polyester resin paint - Google Patents

Abstract

PURPOSE:To provide the titled paint having excellent storage stability and short curing time, consisting of an air-drying unsaturated polyester resin, hollow glass bead having a specified pH and a polymerizable unsaturated monomer. CONSTITUTION:An unsaturated polybasic acid such as maleic anhydride, a polyhydric alcohol such as ethylene glycol and a polyhydric alcohol allyl ether such as pentaerythritol triallyl ether serving as an air drying component are subjected to a polycondensation reaction to obtain an air-drying unsaturated polyester resin (A). 1-20wt% hollow glass bead having an average particle size of 10- 30mu, a true specific gravity of 1-0.1g/cm<3> and a pH of 11 or below is added to an air-drying unsaturated polyester resin paint obtd. by dissolving component A in a polymerizable unsaturated monomer such as styrene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an air-drying unsaturated polyester paint.

Air-drying unsaturated polyester resin paints are made by blending polymerizable unsaturated monomers with resins that are mainly combined with polybasic acids, polyhydric alcohols, and air-drying components, and are used as hardening agents, radical generators, and curing accelerators. It uses metal salts of higher fatty acids and is crosslinked and cured by light or thermal energy. The paint is useful as a paint for general woodworking, as a putty for automobile repair, and as a sealant for joints in buildings, inset parts of glass around sashes, etc.

Various pigments and fillers are usually added to the above paints in order to improve the physical properties of the paint film and reduce costs. ), it is recommended to use hollow glass beads, which exhibit excellent effects in terms of thermal shock resistance, heat insulation, dimensional stability, etc.

However, the present inventor has investigated that when using the beads, depending on the type of polyester paint, the viscosity increases over time, resulting in poor storage stability and difficulty in coating workability. In order to prepare paints that are always stable in terms of quality, the types of chemicals used in paint preparation, their mixing ratios,
It has become clear that there is an inconvenience in that careful attention must be paid each time to the blending method, etc.

However, when producing a polyester paint using hollow glass beads, the present inventor aims to obtain a paint with stable quality without using any special preparation method, by eliminating the cause of the beads making the paint unstable. As a result of investigation, it was found that the pH value of the beads did not have a very large effect on stability, and when beads with a pH of 11 or less were used, a coating material with both curing speed and storage stability within a practical range was obtained. They found that it can be obtained and completed the present invention.

That is, the present invention provides an air-drying unsaturated polyester resin, PHI
It is a paint consisting of hollow glass beads below I and a polymerizable unsaturated monomer, and its characteristics are as described above.
I or less preferably 7 to 10 hollow glass beads are used. If the pH value is 11 or more, the storage stability becomes extremely poor and it is impractical. Furthermore, although it is possible to bring the storage stability within a practical range by adding various stabilizers that have a polymerization inhibiting effect, in this case the curing speed is significantly reduced and the composition is still impractical.

PH as used in the present invention means 5g of hollow glass beads mixed with 1 part of distilled water.
00g, and after 30 minutes of dispersion, the liquid was filtered and the pH of the filtrate was measured.

Among the various commercially available hollow glass beads with double specific PH values, those with PH II or less can be added to the paint of the present invention as they are, but those with a pH of 11 or higher can be treated with acid to reduce the PH to 11. It must be used after completing the following questions.

The hollow glass beads used in the present invention have an average particle size of 1
Those having a range of 0 to 300 microns and a true specific gravity of 1 to 0.1 g/cl are preferably used, and are added in a proportion of about 1 to 20% by weight based on the unsaturated polyester resin.

In preparing the air-drying unsaturated polyester resin, an unsaturated acid is used as the polybasic acid, and a saturated acid is used if necessary.

C is an unsaturated acid, for example, maleic anhydride, maleic acid,
Examples include fumaric acid, itaconic anhydride, -(cuconic acid), and saturated acids include phthalic anhydride, phthalic acid, terephthalic acid, isophthalic acid, henic acid, 7dipic acid, and te1'5.
Examples include hydrophthalic anhydride.

In addition, C is a polyhydric alcohol that can be condensed with a nucleic acid,
ethylene glycol, ) Robylene glycol, diethylene glycol, l-diethylene glycol, dipropylene glycol, bisphenol dioxypropyl ether, 1,3-butylene glycol, 2,3-bunalene glycol, neopentyl glycol, trimesalol propane , glycerin, etc.

Furthermore, examples of polyhydric alcohol ethers used as air-dried components in condensation polymerization include pentaerythritol triallyl ether, trimethylolpropane diallyl ether, chrycerin monoallyl ether, trimethylolethane diallyl-thyl, and glycerin diallyl ether. can give. Both are ethers containing at least 11]M hydroxyl groups in the molecule. The content of allyl group is 0.0 as allyl group per 1 mole of acid component.
A suitable amount is 5 to 2 mol, preferably 0.1 to 1.5 mol.

The air-drying unsaturated polyester resin of the present invention is mixed with a polymerizable unsaturated monomer and used for paints.

Examples of the monomer include styrene, vinyllutoluene, chlorostyrene, α-methylstyrene, divinylhensen,
All crosslinking monomers such as (meth)acrylic acid ester, glycine methacrylate, vinyl acetate, diallyl phthalate, vinyl pyrrolidone, ethylene diacrylate, hydrogochenal nitride, and 'r1P-triacrylate are used. used. Other paint additives that may be used as necessary include pigments, fillers, curing agents, curing accelerators, stabilizers, diluents, and thermoplastic resins.

Municipal materials include (J titanium white, cyanine blue, chrome yellow, watching throat, pen color, carbon black, and aniline black).

Examples of fillers include calcium carbonate, clay, curcum, mica, asbeth (powder, finely divided silica, barium sulfate, zinc stearin, lithopone, etc.).

The curing agent is a compound that easily generates radicals when exposed to heat or ultraviolet light, such as methyl ethyl chloride peroxide,
Examples include cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide, and tertiary-butyl perbenzoate.

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

Stabilizers include hydroquinone, hydroquinone monomethyl ether, toluhydroquinone, P-benzoquinone, 2,5-ditertiary-butylbaraquinone, 2,5
Examples include -ditertiary-amylhydroquinone, 2,5-ditertiary-butylhydroquinone, monotertiary-butylhydroquinone, 2,6-ditertiary-butyl para-cresol, and tertiary-butylcatechol.

Diluents include ethyl acetate, toluene, xylene, methanol, ethanol, butanol, acetone, and MIB.
K, MEK, cellosolve, diacetone alcohol, and the like.

〃) For plasticity j11! Toshi C is cellulose acetate phthalate, nitrocellulose, salt vinyl acetate It III? ,
Vinyl acetate tree 11117, acrylic resin and its copolymerized resin,
Examples include dithylated melamine and butylated urea.

Other additives include phosphorous acid, tartaric acid, phosphorous acid, oil MFIs, silicone mail, W surface activator furnace, and paraffin socks.

The coating of the present invention, the means for applying r4, is particularly suitable for IIM
Any method can be employed, such as the coating method, brush coating method, curfew flow coating method, roll coating method, etc.

Next, the coating material of the present invention will be explained in more detail by giving examples.

Fruit (many)

Air-drying unsaturated polyester tree III (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., Goselac Ni-309B) 372g1
Styrene 64g, P) f 8.0 hollow glass beads (average particle size 70μ, true specific gravity 0.28+1/c++l
), 20 g of titanium oxide, 510 g of talc, 8 g of cobalt octenoate, and 0.05 ff of hydroquinone were added and kneaded in a kneader to make putty for self-governing and others.

Heat this putty to 80 degrees Celsius! The sample was placed in tank A and the number of days until a part of it was cured was measured. (Storage Standard 111) Furthermore, cyclohexyl non-peroxide (Cybox PL, oral medicine^?1FI) was added to the above putty at 42.0% color.
After adding and kneading, the time until hardening was measured. (Measurement ■) After preparing the putty, it was left to stand for 60 days, and then 2.0% by weight of cyclohexanone peroxide was added and the curing time was measured in the same manner. (/pl) These results are shown in the table below. The same procedure was performed on the same side. The results are shown in the table.

Control Examples 1 to 2 In Example 1, hollow glass beads of P H11,11 were used (Control Example 1), and the stabilizer lees were added to P H111.
(Comparative Example 2) was subjected to the same experiment in which the amount of ffsl was increased from 0.05 g to 0.5 g.

Please report those results.

The storage stability of Comparative Example 2 is practical! ! Ii
As mentioned in question I, the curing time is extremely long, making it impractical.

Claims (1)

[Claims] An air-drying unsaturated polyester resin coating consisting of an air-drying unsaturated polyester resin, hollow glass beads with a pH of 11 or less, and a polymerizable unsaturated monomer.