JPH0796593B2 - Unsaturated polyester resin composition for color vehicle - Google Patents

Description

TECHNICAL FIELD The present invention relates to an unsaturated polyester resin composition for a color vehicle, and more specifically, to pigment dispersibility, compatibility, weather resistance and kneading workability at the time of coating. It relates to an excellent unsaturated polyester resin composition for a color vehicle.

[Prior Art] Conventionally, a color vehicle based on an unsaturated polyester resin has been widely used as a coloring agent for paints for decorative plywood, woodworking paints, FRP gel coats and the like. As properties of this base resin, it is important that it has excellent pigment dispersibility and compatibility with other resins, and that it does not cause curing inhibition, and that it is a cured product (product) containing a color vehicle. Has excellent weather resistance (no discoloration) and excellent kneading workability when it is made into a paint [solvents (styrene, other organic solvents) as much as possible when kneading the base resin and pigment. It is required that the distributed work be carried out promptly without using it.

However, conventionally used unsaturated polyester resin compositions for color vehicles do not always satisfy these conditions. For example, since the resin viscosity is high, it cannot be sufficiently kneaded unless it is partially diluted with styrene when it is made into a paint, and the paint with the color vehicle causes color separation in a few days and the original color tone is obtained even when redispersed. There was a problem that it did not come out, and when the cured product (product) was left outdoors, discoloration, deterioration of gloss, etc. occurred within a few months.

[Problems to be solved by the invention]

An object of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to provide an unsaturated polyester resin composition for a color vehicle, which is excellent in pigment dispersibility, compatibility, weather resistance, and kneading workability during coating. .

[Means for solving problems]

As a result of earnest research, the present inventors have diluted an oil-modified unsaturated polyester resin containing a drying oil or semi-drying oil having an iodine value of 120 or more as an oil component at a constant ratio with dibutyl malate having a low volatility. Furthermore, they have found that the above-mentioned object can be achieved by using an ultraviolet absorber for the purpose of preventing yellowing and reduction of gloss during outdoor exposure, and have reached the present invention.

The present invention is an unsaturated polyester resin composition for a color vehicle, which comprises an oil-modified unsaturated polyester (A), a polymerizable monomer (B) and an ultraviolet absorber (C). Viscosity of saturated polyester (A) diluted with dibutylmalate to a heating residue of 65% by weight (Gardner, 25
(° C) is 4 to 30 poise and acid value is 50 or less, and (2) a drying oil or semi-drying oil having an iodine value of 120 or more as an oil component of the unsaturated polyester (A) is removed by condensation water. The unsaturated polyester resin is used in an amount of 2 to 15% by weight, and (3) as the polybasic acid of the unsaturated polyester (A),
A molar ratio of unsaturated acid to saturated acid (unsaturated acid: saturated acid) 1 to
Used in a ratio of 0.3: 0 to 0.7, (4) the polymerizable monomer (B) is dibutyl maleate obtained by an ester condensation reaction of butanol and maleic acid or its anhydride, and the unsaturated polyester The weight ratio (unsaturated polyester: polymerizable monomer) of (A) and the polymerizable monomer (B) is 90 to 40:10 to 60, (5) the ultraviolet absorber (C) Relates to an unsaturated polyester resin composition for a color vehicle containing 0.01 to 5.0% by weight of the unsaturated polyester (A).

The unsaturated polyester resin composition for a color vehicle of the present invention contains an oil-modified unsaturated polyester (A), a polymerizable monomer (B) and an ultraviolet absorber (C).

Oil-modified unsaturated polyester (A) used in the present invention
Has a viscosity (Gardner, 25 ° C.) of 4 to 30 poise when diluted with dibutylmalate to a heating residue of 65% by weight, and an acid value of 50 or less.

If the viscosity is less than 4 poise, curing inhibition occurs when used as a color vehicle because of its small molecular weight.
If the water resistance and weather resistance are reduced and the porosity exceeds 30 poises, it becomes difficult to disperse the pigment due to the high viscosity when it is made into a paint (production of color vehicle).

When the acid value of the unsaturated polyester exceeds 50,
When used as a color vehicle, the water resistance is reduced, and the color vehicle using carbon black undergoes partial gelation over time.

As the oil component of the oil-modified unsaturated polyester (A) of the present invention, a drying oil or a semi-drying oil having an iodine value of 120 or more is used.

When the iodine value of the oil component is less than 120, the dispersibility in carbon black is poor, and when a black color vehicle made of carbon black and a white color vehicle made of titanium white are mixed and used, color unevenness occurs.

As a drying oil or semi-drying oil having an iodine value of 120 or more,
Soybean oil, linseed oil, dehydrated castor oil, safflower oil,
Transesterified oils obtained from cottonseed oil, tung oil, etc. and fatty acids thereof are used.

The oil component is used so as to be contained in the unsaturated polyester in an amount of 2 to 15% by weight, preferably 3 to 10% by weight, as the amount of condensed water removed. If this proportion is less than 2% by weight, the dispersibility of carbon black, cyanine blue, etc. will deteriorate, and if it exceeds 15% by weight, the weather resistance and water resistance when used as a color vehicle will deteriorate.

As the polybasic acid of the oil-modified unsaturated polyester (A) used in the present invention, a molar ratio of unsaturated acid and saturated acid (unsaturated acid: saturated acid) 1 to 0.3: 0 to 0.7, preferably 1 to 0.5: 0
Use at a ratio of ~ 0.5.

If the saturated acid content exceeds 0.7 mol, the curability will decrease when used as a color vehicle, and the water resistance and chemical resistance of the coating film will decrease.

Examples of unsaturated acids include maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like.

Examples of the saturated acid used as necessary include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, het acid, adipic acid, sebacic acid, benzoic acid and the like.

Examples of polyhydric alcohols to be subjected to ester condensation reaction with these polybasic acids include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butyl glycol, 2,3-butylene glycol, neopentyl glycol. , Trimethylolpropane, pentaerythritol and the like.

The oil-modified unsaturated polyester used in the present invention is obtained by subjecting the oil component, the polybasic acid and the polyhydric alcohol to a polycondensation reaction by a conventional method. For example, the polybasic acid and the polyhydric alcohol may be contained in an amount of 150 to 150 so that one or more of the oil components are contained in the unsaturated polyester in a proportion of 2 to 15% by weight as the amount of condensed water removed. After polycondensation at 220 ° C. or after precondensation reaction of the polybasic acid and the polyhydric alcohol at 150 to 200 ° C., these oil components are added to further add 150 to 2
Allow condensation reaction at 20 ℃.

Oil-modified unsaturated polyester (A) used in the present invention
Can also be modified with, for example, an epoxy resin, a polybutadiene resin, a petroleum resin, or the like.

The polymerizable monomer (B) used in the present invention is dibutyl maleate obtained by an ester condensation reaction of butanol and maleic acid or its anhydride, and the unsaturated polyester (A) and the polymerizable monomer. The weight ratio with (B) (unsaturated polyester: polymerizable monomer) is 90 to 40:10 to 60,
It is preferably 85 to 50:15 to 50.

Dibutyl maleate is preferable because it has low volatility and is inexpensive, and particularly has low skin irritation. On the other hand, for example, styrene, vinyltoluene, α-methylstyrene,
In the case of color vehicles using other polymerizable monomers such as methacrylic acid ester and acrylic acid ester, these monomers scatter during long-term storage, and the viscosity of the color vehicle increases, Since the monomer has a copolymerization reactivity with the unsaturated polyester, gelation occurs due to long-term storage.

Further, in place of the maleic acid of dibutyl maleate or its anhydride, there are dibutyl fumarate, dibutyl itaconate and the like, which are composed of fumaric acid, itaconic acid, etc., but these esters are expensive or have a skin irritation. It is large and may cause a rash during handling work.

The dibutyl maleate used in the present invention is obtained by subjecting 2 mol or more of n-butanol and 1 mol of maleic acid or its anhydride to an ester condensation reaction in the presence of a metal catalyst by an ordinary method. At this time, as the metal catalyst, dibutyl titanate, lead acetate or the like can be used.

The ultraviolet absorber (C) used in the present invention is 0.01 to 5.0% by weight with respect to the oil-modified unsaturated polyester (A).
It is preferably contained in a proportion of 0.02 to 3.0% by weight.

If this amount is less than 0.01% by weight, the effect of absorbing ultraviolet rays is small, it turns yellow when exposed to the outdoors, the gloss decreases, and 5.0
Even if it exceeds the weight%, the effect is not particularly remarkable, and it is expensive and impractical.

Examples of the ultraviolet absorber used in the present invention include phenyl salicylate, salicylic acid type ultraviolet absorbers such as 4-t-butylphenyl salicylate, such as 2,4-cihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, Benzophenone-based absorbents such as 2'-hydroxy-4,4'-dimethoxybenzophenone and 2,2'-4,4'-tetrahydroxybenzophenone, for example, 2
(2'-Hydroxy-3,5'-dipentylphenyl) benzotriazole, 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 (2'-hydroxy-4'-n-octyloxyphenyl) benzo Examples thereof include benzotriazole-based absorbents such as triazole.

A color vehicle is obtained by blending a coloring pigment and a filler with the unsaturated polyester resin composition for a color vehicle of the present invention. Examples of the coloring pigment used in this case include titanium white, red iron oxide, aniline black, carbon black, cyanine blue, manganese blue, iron black, ultramarine blue, Hansalet, chrome yellow, chrome green, mapico yellow and the like. Examples of the filler include calcium carbonate, kaolin, clay, alumina, talc, mica and the like. These color pigments and fillers are mixed and dispersed with the unsaturated polyester resin composition using a three-roll, a dissolver, a ball mill, a sand mill and the like.

The color vehicle is added to the unsaturated polyester resin for decorative plywood or FRP gel coat at a ratio of 0.1 to 30% by weight, and as a promoter, for example, metal soaps such as cobalt naphthenate, cobalt octenoate, and manganese octenoate, It is cured by using amines such as dimethylaniline and diethylanine and, for example, methyl ethyl ketone peroxide, cumene hydroperoxide, benzol peroxide and the like as a curing agent.

〔The invention's effect〕

The unsaturated polyester resin composition for a color vehicle of the present invention is excellent in pigment dispersibility and compatibility, and does not cause curing inhibition when used for a decorative plywood paint, a woodwork paint, a FRP gel coat, etc. as a colorant, Further, it does not cause yellowing of the cured product, has excellent weather resistance, has excellent kneading workability when it is made into a coating, and has excellent storage stability during long-term storage.

The unsaturated polyester resin composition for a color vehicle of the present invention can be used not only as a colorant for FRP gel coats, woodwork paints, etc., but also as a colorant for urethane paints, baking paints, etc.

〔Example〕

 Hereinafter, the present invention will be described with reference to examples.

Parts and% in the following examples mean parts by weight and% by weight.

Production Example 1 (Production of transesterified oil (I)) equipped with a stirrer, gas introduction pipe, temperature system and reflux condenser
In a 2l four-necked flask, linseed oil (iodine value 170) 1200
Parts, 300 parts of glycerin and 0.5 parts of lead acetate were added, heated to 220 ° C. for 2 hours while blowing nitrogen gas, and 1 g of the contents in the kettle were dissolved in 2 g of methanol at the same temperature every time (25 The end point was when (° C.) became transparent. 220 ° C
It took 1.5 hours.

Production Example 2 (Production and Comparison of Transesterified Oil (II)) The same procedure as in Example 1 was carried out using 1200 parts of coconut oil (iodine number 7), 300 parts of glycerin and 0.5 part of lead acetate. 220 ° C
After heating for 2.0 hours, it became transparent.

Production Example 3 (Production of oil-modified unsaturated polyester (a)) Using the same apparatus as in Production Example 1, 100 parts (0.28 mol) of the transesterified oil (I) obtained in Production Example 1 and 148 parts of phthalic anhydride ( 1 mol), fumaric acid 580 parts (5 mol), dipropylene glycol 884.4 parts (6.6 mol) and hydroquinone
Add 0.2 parts, raise the temperature from 150 ℃ to 200 ℃ in 3 hours, sample at each time at the same temperature, and heat the viscosity of dibutyl malate diluted to 65% (Gardner, 25
C.) and acid value were measured. After heating at 200 ° C., the viscosity was 10.2 poise and the acid value was 36.5 within 4 hours. 158 g of condensed water was distilled.

Production Example 4 (Production of oil-modified unsaturated polyester (b)) 180 parts of the transesterified oil (I) obtained in Production Example 1 (0.51
Mol), 222 parts (1.5 mols) of phthalic anhydride, 441 parts (4.5 mols) of maleic anhydride, 844.2 parts (6.3 mols) of dipropylene glycol and 0.2 parts of hydroquinone were added and the mixture was heated to 200 ° C. in the same manner as in Production Example 3. It heated and measured the viscosity and acid value. Viscosity 9.2 poise, acid value 27.8 in 5 hours after heating to 200 ℃
showed that. 83 g of condensed water was distilled.

Production Example 5 (Production of oil-modified unsaturated polyester (c)) 144 parts (0.51 mol) of linseed oil fatty acid (iodine value 175), 148 parts (1 mol) of phthalic anhydride, 580 parts (5 mol) of fumaric acid, diester Propylene glycol (916 parts, 6.84 mol) and hydroquinone (0.2 parts) were added and the same as in Production Example 3 at 200 ° C.
The mixture was heated to the temperature and the viscosity and acid value were measured. After raising the temperature by 200 ℃,
After 6 hours, it had a viscosity of 12.8 poise and an acid value of 28.7. Condensation water
192g was distilled.

Production Example 6 (Production and comparison of oil-modified unsaturated polyester (d)) 180 parts of transesterified oil (II) obtained in Production Example 2 (0.64
Mol), 222 parts (1.5 mol) of phthalic anhydride, 441 parts (4.5 mol) of maleic anhydride, 844.2 parts (6.3 mol) of dipropylene glycol and 0.2 parts of hydroquinone, and heated to 200 ° C. in the same manner as in Production Example 3. The viscosity and acid value were measured. After heating at 200 ℃, viscosity is 12.1 poise and acid value is 22.8 in 7 hours.
showed that. 198 g of condensed water was distilled.

Production Example 7 (Production of Dibutylmalate) Using the same apparatus as in Production Example 1, 588 parts of maleic anhydride (6
Mol), n-butanol 950 parts (12.84 mol), dibutyl titanate 5 parts and toluene 10 as a circulating solvent.
After adding 0 part, the temperature was raised to 80 ° C, the dehydration condensation reaction was further advanced, and the temperature was raised to 140 ° C in 2 hours. After heating at this temperature for 12 hours, a reaction product having an acid value of 0.9 was obtained, and heated again to 160 ° C. Then, the circulation toluol was removed.

Examples 1 to 5 and Comparative Examples 1 to 6 (Preparation of unsaturated polyester resin composition) The oil-modified unsaturated polyesters obtained in Production Examples 3 to 5 and Production Example 6 (comparative) were obtained in Production Example 7, respectively. The resulting dibutyl maleate was diluted to a heating residue of 65% by weight, and was further used as an ultraviolet absorber, TINUVIN P [2 (2'-hydroxy-3,5'-dipentylphenyl) benzotriazole, manufactured by Cibagaggy. ] Was added to the oil-modified unsaturated polyester in a ratio shown in Table 1 to obtain an unsaturated polyester resin composition.

Test Example (Adjustment and Test of Color Vehicle) Using the unsaturated polyester resin compositions of Nos. 1 to 13 in Table 1, a color vehicle having the following composition was prepared.

Color vehicle (1) 100 parts of unsaturated polyester resin composition 10 parts of carbon black (MA-100, manufactured by Mitsubishi Kasei Co., Ltd.) were kneaded 3 times with a triple roll.

Color vehicle (2) 60 parts of unsaturated polyester resin composition 60 parts of titanium white (R-930, manufactured by Fuji Titanium Co., Ltd.) were kneaded twice with a three-roll mill.

The following tests were carried out using the color vehicle thus obtained, and the results are shown in Table 2.

(1) Dispersibility test: 5 g of color vehicle (1) and 5 g of color vehicle (2)
A commercially available FRP gel coat clear sample (Polyset-680
P Hitachi Chemical Co., Ltd.) 30 parts, after uniformly dissolving,
0.4 part of Permec N (manufactured by NOF CORPORATION) as a curing agent was added. Immediately after completely melting, flow coat (about 20 g) onto a glass plate immediately, leave at 45 ° angle for 5 hours at room temperature (25 ° C), and visually observe the state of dispersion of the cured coating film. The following criteria evaluated.

⊚: Dispersed uniformly in black and gray.

◯: Black is slightly floating on black and gray.

Δ: Black and white are extremely separated.

X: Black and white are separated.

(2) Weather resistance test: 20 parts of color vehicle (2), 170 parts of commercially available FRP gel coat clear coating (Polyset-680P), 10 parts of styrene and 1.5 parts of Permec N as a curing agent were completely dissolved,
Degas in a vacuum (about 2 to 3 minutes) and immediately return to an inner diameter of 0.
It is poured into an iron casting plate measuring 8 cm × 30 cm × 30 cm,
℃) for 3 hours, then at 60 ℃ 16 to further cure
Dried for hours. Then, the cured coated plate was put in a Ducycle weather meter (manufactured by Suga Test Instruments Co., Ltd.), and a color difference meter (manufactured by Nissha Co., Ltd.) and a gloss meter (manufactured by Stanken Co., Ltd.) were used to show discoloration with time (0 hours). The color difference with ΔE) and the gloss reduction rate (%) were measured.

(3) Boiling resistance test: The coated plate obtained in (2) was put in boiling water (100 ° C.), and the coated surface state (blister) was observed and evaluated according to the following criteria.

○: No abnormality.

9F: Blisters of about 1 mm occur on about 5% of the coated surface.

8D: A blister of about 2 mm has occurred on the entire painted surface.

6D: A blister of about 4 mm has occurred on the entire painted surface.

From the results shown in Table 2, it is shown that in the case of Examples, the pigment dispersibility is excellent and the cured product is also excellent in weather resistance.

Claims (1)

[Claims] 1. An unsaturated polyester resin composition for a color vehicle, comprising an oil-modified unsaturated polyester (A), a polymerizable monomer (B) and an ultraviolet absorber (C), (1) Viscosity of unsaturated polyester (A) diluted with dibutyl maleate to a heating residue of 65% by weight (Gardner, 25
(° C) is 4 to 30 poise and acid value is 50 or less, and (2) a drying oil or semi-drying oil having an iodine value of 120 or more as an oil component of the unsaturated polyester (A) is removed by condensation water. 2 to 15% by weight in the unsaturated polyester as
(3) As the polybasic acid of the unsaturated polyester (A),
A molar ratio of unsaturated acid to saturated acid (unsaturated acid: saturated acid) 1 to
(4) The polymerizable monomer (B) is dibutyl maleate obtained by ester condensation reaction of butanol and maleic acid or its anhydride, and the unsaturated polyester. The weight ratio (unsaturated polyester: polymerizable monomer) of (A) and the polymerizable monomer (B) is 90 to 40:10 to 60, (5) the ultraviolet absorber (C) Is an unsaturated polyester resin composition for a color vehicle, which is contained in an amount of 0.01 to 5.0% by weight based on the unsaturated polyester (A).