JP2002265861A - Unsaturated polyester resin paint - Google Patents

Abstract

(57) [Problem] To provide an unsaturated polyester resin paint having significantly reduced whitening of a coating film even in a high humidity atmosphere while maintaining curability and polishing property of the coating film. (A) A polyhydric alcohol containing at least two kinds of aliphatic polyhydric alcohols having 4 or less carbon atoms having a branched structure and an aliphatic polyhydric alcohol having 5 or more carbon atoms having a branched structure, (B) An unsaturated polyester resin paint containing an unsaturated polyester resin obtained by reacting a polybasic acid and (C) a polyhydric alcohol allyl ether,
In particular, the aliphatic polyhydric alcohol having a branched structure and having 4 or less carbon atoms used as the component (A) is 2-methyl-1,3-
Propanediol, 1,2-propanediol, 1,3
-Two kinds of aliphatic polyhydric alcohols having a branched structure and having 5 or more carbon atoms selected from butanediol are 3-methyl-
It is an unsaturated polyester resin paint which is 1,5-pentanediol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester resin paint, and more particularly, to an unsaturated polyester resin paint which hardly whitens even under a high humidity atmosphere while maintaining the curability and abrasiveness of the paint film. The present invention relates to a polyester resin paint.

[0002]

2. Description of the Related Art Unsaturated polyester resin paints containing a polyhydric alcohol allyl ether component have been conventionally used in general (for woodworking) because they have an air-drying property, are preferably glossy and have a solid feeling, and have a beautiful finish. ) Used for paints, sealing materials, etc. In applications such as building materials and furniture, such an unsaturated polyester resin paint is often used as an intermediate coating. In this case, the unsaturated polyester resin paint is applied to a substrate, cured, then polished. After improving the smoothness, a top coat such as a urethane resin paint is applied thereon.

[0003]

However, when the unsaturated polyester resin paint is exposed to a high-humidity atmosphere, a whitening phenomenon may occur in the coating film. As described above, since the unsaturated polyester resin paint is used for the intermediate coating, such a drawback does not seem to be a big problem, but the cut surface cross section and the end portion of the coating film surface, and further the application of the top coating paint. The whiteness may occur due to the invasion of moisture from the back surface of the base material that has not been performed, and the commercial value may be reduced.

[0004] In order to solve such problems, the present inventors focused on the composition of unsaturated polyester resin and reacted polybasic acid and polyhydric alcohol allyl ether using a polyhydric alcohol having a branched structure. It was confirmed that the unsaturated polyester resin obtained as described above was effective. However, the coating film obtained above may have poor curability and abrasiveness, and the unsaturated polyester resin coating film must originally hold, without impairing such properties, solving the prevention of whitening. It turned out that we had to. An unsaturated polyester resin paint using a polyhydric alcohol having a branched structure as a condensation component is described in, for example, JP-A-2000-239364.
The above-mentioned problem could not be solved within the scope disclosed in this publication.

[0005]

Accordingly, as a result of intensive studies conducted by the present inventors, when the above-mentioned specific combination of aliphatic polyhydric alcohol having a branched structure is selected,
The present inventors have found that prevention of whitening, improvement in curability and polishing properties can be exhibited in a well-balanced manner, and completed the present invention. That is, the present invention relates to “(A) a polyhydric alcohol containing an aliphatic polyhydric alcohol having a branched structure and having 4 or less carbon atoms and an aliphatic polyhydric alcohol having a branched structure and having 5 or more carbon atoms,
(B) an unsaturated polyester resin paint containing an unsaturated polyester resin, which is obtained by reacting a polybasic acid and (C) an allyl ether of a polyhydric alcohol, and is particularly used as a component of (A). Aliphatic polyhydric alcohol having a branched structure having 4 or less carbon atoms is 2-methyl-1,3
-Propanediol, 1,2-propanediol, 1,
An aliphatic polyhydric alcohol having 5 or more carbon atoms and having a branched structure and used as one component of (A), which is two kinds selected from 3-butanediol, is 3-methyl-1,5-pentanediol. It is intended to provide an unsaturated polyester resin paint.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The unsaturated polyester resin used in the present invention,
A condensation polymerization product of (A) a polyhydric alcohol, (B) a polybasic acid, and (C) a polyhydric alcohol allyl ether,
(A) is characterized by a combination of at least two kinds of aliphatic polyhydric alcohols having 4 or less carbon atoms having a branched structure and polyhydric alcohols containing aliphatic polyhydric alcohols having 5 or more carbon atoms having a branched structure. Things.

The aliphatic polyhydric alcohol having a branched structure and having 4 or less carbon atoms used as one component of (A) includes:
1,2-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and the like, and 2-methyl-1,3-propanediol, 1,2 -Two kinds selected from propanediol and 1,3-butanediol, particularly 2-methyl-1,3
Combinations of propanediol and 1,3-butanediol and combinations of 1,2-propanediol and 1,3-butanediol are useful.

Examples of the aliphatic polyhydric alcohol having 5 or more carbon atoms having a branched structure and used as a component of (A) include 3-methyl-1,5-pentanediol and 2,2
-Dimethyl-1,3-propanediol and methyloctanediol are mentioned, and 3-methyl-1,5-pentanediol is particularly preferred. When two kinds of aliphatic polyhydric alcohols having 4 or less carbon atoms are used, the amount used is not particularly limited, and is 1/9 to 9/1, preferably 3/7 to 7 / on a molar ratio basis.
3.

The proportion of the aliphatic polyhydric alcohol having 4 or less carbon atoms to the aliphatic polyhydric alcohol having 5 or more carbon atoms is 50 to 95%, preferably 60 to 85%, based on the weight.
The latter is suitably from 5 to 50%, preferably from 15 to 40%. When the amount of the aliphatic polyhydric alcohol having 4 or less carbon atoms is 5
If it is less than 0%, the curability of the coating material will be poor, and if it exceeds 95%, the cured coating film will be hard and brittle, making it impractical.

In the present invention, other polyhydric alcohols are used, if necessary, in addition to the above-mentioned aliphatic polyhydric alcohol having a branched structure. For example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, Hydrogenated bisphenol A, bisphenol A dioxypropoxy ether,
Bisphenol A dipolyoxypropoxy ether, bisphenol A dioxyethoxy ether, bisphenol A dipolyoxyethoxy ether, 1,9-nonanediol, polypropylene glycol, polyethylene glycol, polytetramethylene glycol, 1,4-butylene glycol, 1, 6-hexanediol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, cyclohexanedimethanol and the like can be mentioned.

As the polybasic acid (B), an unsaturated polybasic acid is used as a main component, and a saturated polybasic acid is used as necessary. Examples of the unsaturated polybasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid and the like.Examples of the saturated polybasic acid include phthalic anhydride, phthalic acid, terephthalic acid, isophthalic acid, Het acid, adipic acid, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 6-methyl-4-cyclohexene-1,2,3 And tricarboxylic anhydrides.

In the present invention, in order to impart dryness to the air, the unsaturated polyester resin has the following components:
(C) Polyhydric alcohol allyl ether is used.
(C) As the polyhydric alcohol allyl ether, specifically, pentaerythritol triallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, trimethylolethanediallyl ether,
Glycerin diallyl ether, etc., are all ethers containing at least one hydroxyl group in the molecule.

The proportion of the (C) polyhydric alcohol allyl ether is 10 to 50 mol% based on the polybasic acid component.
In particular, the content is preferably 20 to 40 mol%. If the proportion is less than 10 mol%, sufficient air-drying properties cannot be obtained, while if it exceeds 50 mol%, the curability is reduced.

In the production of the unsaturated polyester resin, the above components may be subjected to a condensation or addition reaction in an inert gas atmosphere at a temperature of about 150 to 250 ° C. according to a conventional method. The unsaturated polyester resin usually has an acid value of about 10 to 30 KOHmg / g,
Preferably, the esterification is promoted to increase the acid value to 10 to 25 KO.
It is preferred to be in the range of about Hmg / g. The weight-average molecular weight of the unsaturated polyester resin is not particularly limited, but is preferably 3,000 to 50,000, more preferably 4,000 to 50,000.
When the weight average molecular weight is less than 3,000, the physical properties of the cured product are low, and the curability is slow.
If it exceeds 0000, the viscosity increases and a large amount of diluent monomer is required, and the curing rate tends to be slow.

The weight-average molecular weight of the present invention is measured by gel permeation chromatography (GPC). For example, using a KF-806 column with a Shodex system (manufactured by Showa Denko KK), tetrahydrofuran is used as a solvent. And polystyrene as a standard.

When the unsaturated polyester resin paint used in the present invention is cured at room temperature or by heating, an organic peroxide, a higher fatty acid cobalt salt or the like is used as a catalyst by irradiation with active energy rays such as ultraviolet rays. When curing, a photopolymerization initiator is blended. As the organic peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t-
Butyl perbenzoate and the like. Examples of the higher fatty acid cobalt salts include cobalt octenoate and cobalt naphthenate, and preferably, methyl ethyl ketone peroxide, cobalt octenoate, and cobalt naphthenate are used.

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxypropyl phenyl ketone, 2-hydroxypropyl-4-isobutyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1-
[4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4 -Phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-chlorothioxanthone
Methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone,
Dibenzosuberone, 2-ethylanthraquinone, 4 ',
4 "-diethylisophthalophenone, 3,3 ', 4
4'-tetra (t-butylperoxycarbonyl) benzophenone, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone and the like. Triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (N-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like can be used in combination. is there

The compounding ratio of such a drug is not particularly limited, but in order to obtain the effect of the present invention efficiently, the compounding ratio of the organic peroxide is 0.1 to 100 parts by weight of the unsaturated polyester resin. 1 to 5 parts by weight, preferably 1 to
3 parts by weight, 0.1 to 2 parts by weight, preferably 0.3 to 0.6 parts by weight of a higher fatty acid cobalt salt (as a metal content of 8% by weight), 0.5 to 6 parts by weight of a photopolymerization initiator, Preferably 1
~ 2 parts by weight.

After applying the unsaturated polyester resin paint obtained in such a composition to a substrate, the paint is applied at room temperature or by heating.
Alternatively, the coating is cured by light irradiation. It is practical that the thickness of the coating film is about 100 to 400 μm, the curing temperature is 20 to 60 ° C., and the curing time is about 4 to 24 hours. The light irradiation with the active energy ray is not particularly limited as long as it is a method of activating the photopolymerization initiator, and electromagnetic waves such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X-rays, γ rays, etc. And electron beam, proton beam, a method of curing by irradiating active energy rays such as neutron rays, etc., but from the availability of radiation irradiation equipment, price, etc., curing method by ultraviolet irradiation is advantageous, The UV is 150-450
mainly composed of light in the nm wavelength range.
Irradiation using a metal halide lamp, a xenon lamp, a chemical lamp, or the like can be given.

The polyester resin film thus obtained is polished and coated with a top coat to produce a product. The paint of the present invention is a paint for coating various base materials,
It can be widely used as a sealing agent, etc., and depending on its use, abrasives (zinc stearate, talc, silica, calcium carbonate, etc.) defoamers, flame retardants, antistatic Agents, plasticizers, pigments (titanium white, cyanine blue, watching red, red iron oxide, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc.), fillers (calcium carbonate) , Kaolin, clay, talc, mica, alumina, asbestos powder, finely divided silica, barium sulfate, lithopone, stone, zinc stearate, perlite, etc.), leveling agent (silicone, cellulose acetate butyrate, surfactant, etc.), stable Agent, thermoplastic resin (high density, medium density, low density Various polyethylene, polypropylene, polybutene, homopolymers such as polypentene of
Polyamide-based resins such as ethylene-propylene copolymer, nylon-6, nylon-6,6, vinyl chloride-based resin,
Nitrocellulose resin, vinylidene chloride resin, acrylic resin, acrylamide resin, styrene resin,
Vinyl ester resin, polyester resin, etc.), reinforcing agent (glass fiber, carbon fiber, etc.), anti-dripping agent (hydrogenated castor oil, fine silica anhydride, etc.), matting agent (fine powder silica,
It is also possible to mix paraffin wax and the like.

As the diluent, styrene, ethyl acetate, toluene, xylene, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolves, diacetone alcohol, acrylates, alkyl vinyl ketones and the like are appropriately used.

[0022]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, "%" and "parts"
Unless otherwise specified, it is based on weight.

Example 1 [Production of unsaturated polyester resin (AI)]
In a reactor equipped with a rectification tower, nitrogen introduction pipe, and vacuum device,
327 parts (4.3 mol) of 2-propanediol, 1,3
-Butanediol 203 parts (2.3 mol), 3-methyl-1,5-pentanediol 243 parts (2.0 mol),
805 parts (8.2 mol) of maleic acid, 420 parts (1.6 mol) of pentaerythritol triallyl ether and 0.02% of hydroquinone were charged, and the reaction was carried out at 190 ° C. for 5 hours in a nitrogen gas atmosphere. went. An unsaturated polyester resin (AI) having an acid value of 25 KOH mg / g and a weight average molecular weight of 25,000 was obtained. The resin was diluted with styrene to a solid content of 65%.

The above unsaturated polyester resin (AI)
80 parts, styrene 20 parts, methyl ethyl ketone peroxide (pure content 55%) 2 parts, cobalt naphthenate (metal content 8%) 0.4 part, abrasive (zinc stearate) 2
Was added to obtain an unsaturated polyester resin paint. Using the obtained unsaturated polyester resin paint, a coating film was formed as described below, and the coating film was evaluated.

(Hardness) The obtained unsaturated polyester resin paint was applied on a glass plate with a 200 μm applicator, dried and cured at 25 ° C. for 24 hours to form a coating film. The pencil hardness of the obtained coating film was measured according to JIS K-5400.

(Abrasiveness) A melamine plate (white, 30 cm.times.30 cm, thickness: 5.times.) Coated with the obtained unsaturated polyester resin paint and urethane sealer as a base material in advance.
5mm, preheated in an oven at 40 ° C for 5 minutes)
After coating at 200 g / m ² by the method, it was dried and cured at 25 ° C. for 24 hours to form a coating film. The obtained coating film was # 40
It was manually polished with 0 paper and evaluated on a 5-point scale as follows. 5: Very good polishing properties 4: Excellent in polishing properties 3: Normal in polishing properties 2: Poor in polishing properties 1: Very poor in polishing properties

(Bleaching) A melamine plate (white, 30 cm × 30 cm, thickness 5.5) to which the obtained unsaturated polyester resin paint was previously coated with a urethane sealer as a base material.
200 g / m < ² > by a spray method, and dried and cured at 25 [deg.] C for 24 hours to form a coating film. Apply the obtained coating film to 60
The film was allowed to stand for 24 hours in an atmosphere of 95 ° C. and 95% RH. 3: no whitening was observed and the film was in a clear state 2: slightly opaque tendency was observed 1: whitening was observed on the entire surface

Example 2 [Production of unsaturated polyester resin (A-II)] 1,2-
405 parts (5.3 mol) of propanediol, 230 parts (2.6 mol) of 1,3-butanediol, 3-methyl-
112 parts of 1,5-pentanediol (0.95 mol),
(AI) except that 498 parts (5.1 mol) of maleic acid, 361 parts (2.2 mol) of 3-methyltetrahydrophthalic anhydride and 372 parts (1.45 mol) of pentaerythritol triallyl ether were used. To obtain an unsaturated polyester resin (A-II) having an acid value of 25 KOH mg / g and a weight average molecular weight of 35,000. The resin was diluted with styrene to a solid concentration of 65%. Using the obtained unsaturated polyester resin (A-II) in the same manner as in Example 1, an unsaturated polyester resin paint was obtained, and a coating film was formed and evaluated in the same manner as in Example 1.

Example 3 [Production of unsaturated polyester resin (A-III)] (A-III) 2-methyl-1,3-propanediol 2
81 parts (3.1 mol), 1,3-butanediol 194
Part (2.2 mol), 81 parts (0.7 mol) of 3-methyl-1,5-pentanediol, diethylene glycol 6
6.2 parts (0.62 mol), 428 parts of maleic acid (4.
4 mol), 3-methyltetrahydrophthalic anhydride 310
Part (1.9 mol) and 639 parts (2.5 mol) of pentaerythritol triallyl ether (A-
The reaction was carried out according to I), and an unsaturated polyester resin having an acid value of 25 KOH mg / g and a weight average molecular weight of 40,000 (A
-III). The resin is styrene with a solid content of 65%
Diluted. The obtained unsaturated polyester resin (A-II
I) was performed in the same manner as in Example 1 to obtain an unsaturated polyester resin paint, and a coating film was formed in the same manner as in Example 1.
An evaluation was performed.

Comparative Example 1 [Production of unsaturated polyester resin (A-IV)] 1,3-
Butanediol 304 parts (3.4 mol), 3-methyl-
553 parts (4.7 mol) of 1,5-pentanediol, 463 parts (4.72 mol) of maleic acid, 336 parts (2.0 mol) of 3-methyltetrahydrophthalic anhydride, 345 parts of pentaerythritol triallyl ether ( The reaction was carried out according to (AI) except that (1.35 mol) was used to obtain an unsaturated polyester resin (A-IV) having an acid value of 25 KOH mg / g and a weight average molecular weight of 35,000. The resin was diluted with styrene to a solid concentration of 65%. Using the obtained unsaturated polyester resin (A-IV), an unsaturated polyester resin paint was obtained in the same manner as in Example 1, and a coating film was formed and evaluated in the same manner as in Example 1.

Comparative Example 2 [Production of unsaturated polyester resin (AV)] 1,2-
Propanediol 312 parts (4.0 mol), diethylene glycol 228 parts (2.2 mol), triethylene glycol 293 parts (2.0 mol), maleic acid 766 parts (7.8 mol), pentaerythritol triallyl ether 400 (A-I) except that part (1.6 mol) was used.
And an unsaturated polyester resin having an acid value of 25 KOH mg / g and a weight average molecular weight of 28,000 (A-
V) was obtained. The resin was diluted with styrene to a solid concentration of 65%. Using the obtained unsaturated polyester resin (AV), an unsaturated polyester resin paint was obtained in the same manner as in Example 1, and a coating film was formed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results of the examples and the comparative examples.

[0032]

The unsaturated polyester resin paint of the present invention is produced from a specific combination of aliphatic polyhydric alcohols having a branched structure, so that high humidity and high curability can be maintained while maintaining the curability and abrasiveness of the coating film. It has the effect that the whitening of the coating film is significantly reduced even in an atmosphere.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J029 AA07 AB04 AC02 AD01 AE11 BA07 BA08 BA09 BA10 CA02 CA06 CB04A CB05A CB06A CD03 FC36 FC41 GA02 GA13 GA14 GA17 HA01 HB01 HB06 4J038 DD181 DD191 DD201 DD221 GA02 NA01 NA04

Claims (3)

[Claims] (A) a polyhydric alcohol containing two or more kinds of aliphatic polyhydric alcohols having 4 or less carbon atoms having a branched structure and an aliphatic polyhydric alcohol having 5 or more carbon atoms having a branched structure, (B) An unsaturated polyester resin paint comprising an unsaturated polyester resin obtained by reacting a polybasic acid and (C) an allyl ether of a polyhydric alcohol. Wherein aliphatic having 4 or less carbon having a branched structure used as a component of (A) a polyhydric alcohol, 2-
2. The unsaturated polyester resin paint according to claim 1, wherein the paint is two kinds selected from methyl-1,3-propanediol, 1,2-propanediol, and 1,3-butanediol. 3. An aliphatic polyhydric alcohol having a branched structure and having 5 or more carbon atoms, which is used as one component of (A), comprises
3. The unsaturated polyester resin paint according to claim 1, wherein the paint is methyl-1,5-pentanediol.