JPH07216073A - Unsaturated polyester resin composition and putty coating compound - Google Patents

Abstract

PURPOSE:To obtain an unsaturated polyester resin composition containing a specific unsaturated polyester and a polymerizable unsaturated liquid compound at a specific ratio, suitable as a binder of a mending putty coating component for automobile, electric car, etc., and having excellent adhesivity to an electrogalvanized plate, moisture resistance, dryability, polishability and toughness. CONSTITUTION:This unsaturated polyester resin composition contains (A) 30-80wt.% of an unsaturated polyester having an acid value of <=50 and a number-average molecular weight of 500-10,000 and produced by reacting (i) a polybasic acid component containing an alpha,beta-unsaturated polybasic acid and other polybasic acid at a molar ratio of (0.30-0.70):(0.70-0.30) and containing a dimer acid at a molar ratio of 0.01-0.10 in the other polybasic acid with (ii) a glycol component containing an ether glycol and other glycol at a molar ratio of (1.00-0.30):(0-0.70) and (iii) allyl glycidyl ether at molar ratios (i):(ii):(iii) of 1.00:(1.50-0.70):(0.05-0.30) and a molar ratio [(ii)+(iii)]:(i) of >=1 and (B) 20-70wt.% of a polymerizable unsaturated liquid compound.

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 composition, and more particularly to an unsaturated polyester resin composition suitable as a binder for a putty paint for repairing automobiles, trains and the like, and a putty paint using the same.

[0002]

2. Description of the Related Art Unsaturated polyester resins are generally cheaper than other resins, and have excellent workability because they cure at room temperature in a short time. Due to its scientific properties,
For example, construction materials such as corrugated sheets, bathtubs, septic tanks, industrial equipment such as tanks, containers and pipes, transportation equipment such as ships and automobiles,
Widely used in various applications such as electrical insulation materials, resin concrete, decorative boards, gel coats, and putty paints. In particular, for putty paints for repairing vehicles such as automobiles and trains, (1) excellent workability with a spatula, (2) quick curing at room temperature, (3) excellent polishability,
(4) Excellent adhesion to the material, (5) Excellent adhesion to the top coating, (6) Excellent moisture resistance, (7) Excellent durability (cracks) Performance is required.

However, in recent years, the materials used for the outer walls of vehicles such as automobiles and trains have been mainly treated with zinc phosphate for the purpose of heavy corrosion protection from iron plates treated with zinc phosphate, iron phosphate, etc. for the purpose of rust prevention. Since the metal used as a component has been transferred to an anti-rust steel plate that has been directly electroprocessed on an iron plate and an aluminum plate for the purpose of weight reduction, repairing with a conventional putty causes adhesion inhibition of the coating,
Peeling, blister etc. occur frequently. In addition, there is an accident that the putty coating film falls off due to vibration because the material that is made of an aluminum plate and expands and contracts greatly during traveling on the outer wall.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a repair putty for automobiles, trains, etc., which is excellent in adhesion to zinc-treated steel sheets and aluminum sheets and is also excellent in durability (cracks), abrasiveness, moisture resistance and dryness. The present invention provides an unsaturated polyester resin composition which can be suitably used as a binder for paints and a putty paint using the same.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies in view of the above problems, the present inventors have found that a polybasic acid component has a certain amount of α, β-unsaturated polybasic acid for accelerating the curing at room temperature. ,
Polybasic acids other than α, β-unsaturated polybasic acids, dimer acid that is presumed to have a relaxation effect on the adhesion to electrozinc treated plates and aluminum plates and the stretching and contraction of coating films due to vibration Allyl glycidyl ether as a certain amount of air-drying component for improving, unsaturated polyester obtained by using a certain amount or more of ether glycol in the glycol component to give further air-drying power when combined with the air-drying component The inventors have found that the above object can be achieved by using an unsaturated polyester resin composition containing (A) and a liquid polymerizable unsaturated compound (B) as a binder of a putty paint, and arrived at the present invention.

That is, the present invention is (A) (a) α, β
-The unsaturated polybasic acid and the polybasic acid other than the α, β-unsaturated polybasic acid are used in a molar ratio of 0.30 to 0.70: 0.7.
0 to 0.30 (α, β-unsaturated polybasic acid: polybasic acid other than α, β-unsaturated polybasic acid), and the polybasic acid other than the α, β-unsaturated polybasic acid , Dimer acid above α, β
-Mole ratio of polybasic acid other than unsaturated polybasic acid (0.70-
0.30) in the range of 0.01 to 0.10. Polybasic acid component, (b) Ether glycol and the glycol other than ether glycol are used in a molar ratio of 1.0.
0 to 0.30: 0 to 0.70 (ether glycol: glycol other than ether glycol), glycol component and formula (c)

[Chemical 2] The allyl glycidyl ether represented by (a) :( b):
The molar ratio of (c) is 1.00: 1.50 to 0.70: 0.
The acid obtained by reacting the glycol component (b) and the allyl glycidyl ether (c) in an amount of 05 to 0.30 in an equimolar amount or more with respect to the polybasic acid component (a). Value 50 or less, number average molecular weight 500-1
30-80% by weight of unsaturated polyester of 50,000
And (B) an unsaturated polyester resin composition containing 20 to 70% by weight of a liquid polymerizable unsaturated compound, and a putty paint containing the unsaturated polyester resin composition as a binder.

The polybasic acid component (a) used in the present invention is composed of an α, β-unsaturated polybasic acid and a polybasic acid other than α, β-unsaturated polybasic acid (hereinafter referred to as polybasic acid X). The molar ratio is 0.30 to 0.70: 0.70 to 0.30, preferably 0.40 to 0.60: 0.60 to 0.40. When the use ratio of the α, β-unsaturated polybasic acid exceeds 0.70 mol, the crosslinking density of the putty coating film becomes high, and when the film thickness is increased, cracks may occur in the coating film and the coating film may fall off. If the amount is less than 0.30 mol, curing at room temperature will be slow, and the drying property and polishing property of the putty coating film will be deteriorated.

In the polybasic acid X, a certain amount of dimer acid is used as an essential component. Dimer acid is unsaturated fatty acid,
For example, it is obtained by polymerizing linoleic acid, linolenic acid and the like in the presence of a catalyst by heating, and is mainly composed of a dimer dicarboxylic acid. The dimer acid has a strong adsorptivity on the metal surface and has a long-chain molecular structure, which is effective in improving crack resistance. Dimer acid is a polybasic acid X,
In the molar ratio of the polybasic acid X (0.70 to 0.30), 0.
The range of 01-0.10, preferably 0.02-0.08
The range is. If the amount of dimer acid used is less than 0.01 at this molar ratio, the adhesion to the raw material will be reduced, and at the same time, cracking will tend to occur if the film thickness is increased, and
When it exceeds 0, the coating film becomes soft and the coating film is likely to be scratched during polishing.

Examples of the polybasic acid X other than dimer acid include phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, het acid, adipic acid and sebacic acid.

Examples of the α, β-unsaturated polybasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like. Two or more kinds of polybasic acids X and α, β-unsaturated polybasic acids other than the dimer acid may be used in combination.

In the glycol component (b) used in the unsaturated polyester (A), the ether glycol is 1.00 to 0.30, preferably 1.0 in the above molar ratio.
The range is from 0 to 0.50. When the molar ratio of ether glycol is less than 0.30, the workability of polishing the putty coating film is deteriorated in combination with the allyl glycidyl ether (c). It is presumed that by combining the allyl glycidyl ether (c) and the ether glycol of (b), a further oxygen absorbing action occurs, and the drying property of the surface of the putty coating film is promoted.

As the ether glycol in the glycol component (b), for example, diethylene glycol, triethylene glycol, dipropylene glycol and the like are used. You may use together 2 or more types of these. As glycols other than ether glycol, for example, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,6-hexane glycol, hydrogenated bisphenol A and the like are used. Glycols other than these ether glycols are used in the glycol component in the range of 0.70 mol or less in the above molar ratio. You may use these 2 or more types together.

In the present invention, in order to impart air-drying property,
A certain amount of allyl glycidyl ether (c) is used. Allyl glycidyl ether has excellent reactivity,
Unreacted components do not remain and can be more completely introduced into the resin skeleton, which improves air-drying properties and at the same time improves adhesion to zinc-treated plates and aluminum plates.

The unsaturated polyester (A) of the present invention is obtained by reacting a polybasic acid component (a), a glycol component (b) and an allyl glycidyl ether (c) and has an acid value of 5
0 or less, preferably 30 or less and a number average molecular weight of 50
It is adjusted to be 0 to 10,000, preferably 800 to 5,000. In order to adjust the acid value and the number average molecular weight in this range, the polybasic acid component (a), the glycol component (b) and the allyl glycidyl ether (c) are mixed at a molar ratio ((a) :( b) :( c)). ) At 1.00: 1.50
.About.0.70: 0.05 to 0.30, and the total number of moles of the glycol component (b) and the allyl glycidyl ether (c) is equal to or more than the mole number of the polybasic acid component (a). To be done.

The above molar ratio of the polybasic acid component (a) is 1.
When the number of moles exceeds 00 and is less than the total number of glycol components (b) and allyl glycidyl ether (c), the unsaturated polyester (A) has an acid value of more than 50, which significantly reduces the water resistance of the putty coating film. . Further, when the above-mentioned molar ratio of the glycol component (b) exceeds 1.50, the number average molecular weight of the unsaturated polyester (A) becomes less than 500, and the putty coating film exhibits curability, crack resistance, chemical resistance and the like. descend. When it is less than 0.70, the number average molecular weight of the unsaturated polyester (A) exceeds 10,000, the workability of putting putty is deteriorated, and at the same time, the amount of the liquid polymerizable unsaturated compound (B) used is increased, and The coating film deteriorates. If the use ratio of allyl glycidyl ether is less than 0.05 in the above-mentioned molar ratio, the air-drying property of the putty coating film is not sufficient and the polishing property is remarkably deteriorated. However, the putty coating film becomes soft and the coating film is easily scratched during polishing.

Examples of the liquid polymerizable unsaturated compound (B) used in the present invention include aromatic vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, t-butylstyrene and divinylbenzene, and acrylic. Examples thereof include acrylic acid or methacrylic acid compounds such as methyl acidate, methyl methacrylate, glycidyl methacrylate, and 2-ethylhexyl methacrylate. You may use these together.

The unsaturated polyester resin composition of the present invention contains 30 to 80% by weight of the unsaturated polyester (A).
And the above liquid polymerizable unsaturated compound (B) 20 to 7
Contains 0% by weight. When the compounding ratio of the liquid polymerizable unsaturated compound (B) is less than 20% by weight, the reaction with the unsaturated polyester (A) is not sufficient, a coating film having high hardness cannot be obtained, and the putty coating film can be polished. At this time, the coating film is likely to be scratched, and when it exceeds 70% by weight, the putty coating film has poor wall-holding property, and the curability and adhesion are deteriorated.

The unsaturated polyester (A) used in the present invention can be obtained by a conventional method. For example, the polybasic acid component (a) and the glycol component (b) are added at 150 ° C to 2
A polycondensation reaction is carried out at 20 ° C., and then, as a ring-opening reaction catalyst of allyl glycidyl ether (c) and epoxy group,
Add 0.05 to 5.0% by weight of a primary ammonium salt (eg, tetraammonium chloride, dimethyldodecylbenzylammonium chloride, etc.) or an alkali metal salt (eg, potassium benzoate, sodium benzoate, etc.) to allyl glycidyl ether. , 80 ℃ ~
It is obtained by carrying out a ring-opening addition reaction at 180 ° C.

When the resin composition of the present invention is used as a putty paint, if necessary, a filler, a color pigment, a curing accelerator and the like are kneaded by a three roll roll, a dissolver or the like and blended. Examples of the filler include talc, mica, kaolin, calcium carbonate, clay and the like. The filler is usually used in the putty paint in an amount of 30 to 80% by weight.
Examples of the color pigment include titanium white, red iron oxide, aniline black, carbon black, cyanine blue, manganese blue, iron black, chrome yellow, chrome green, mapico yellow and the like. The coloring pigment is usually used in the putty paint in an amount of 1 to 10% by weight. Examples of the curing accelerator include cobalt naphthenate, cobalt octenoate,
Examples thereof include metal soaps such as manganese octenoate and amines such as dimethylaniline and diethylaniline.
The amount of the curing accelerator used is usually 0.2 to 5 in the putty paint.
Used by weight percent. When applying the above paint (putting putty)
In, a curing agent is mixed and dispersed. The curing agent is usually used in the putty paint in an amount of 1 to 4% by weight. As the curing agent, methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, etc. are used.

[0020]

EXAMPLES Examples of the present invention will be described below. The parts and% in the following examples mean parts by weight and% by weight, respectively. Example 1 Diethylene glycol 8 was placed in a 2 liter four-necked flask equipped with a stirrer, gas inlet tube, thermometer and reflux condenser.
16.2 g (7.70 mol), Versadim 2162
03.7 g (0.35 mol) (General Mil
ls. Inc. trade name, dimer acid, molecular weight 582)
Further, 406.7 g (2.45 mol) of isophthalic acid was charged, the temperature was raised from 150 ° C. to 220 ° C. in 4 hours, and heated at the same temperature until the acid value of the contents in the kettle became 50 to 45. After heating to 220 ° C. and heating for 1.5 hours, the acid value became 46.9. It is then cooled to 80 ° C. and maleic anhydride 41
1.6 g (4.20 mol), allyl glycidyl ether 1
As a ring-opening catalyst for 59.6 g (1.40 mol) allyl glycidyl ether, 0.45 g of potassium benzoate, 0.2 g of hydroquinone and 40 g of xylol for reflux were charged, and the mixture was kept at 90 ° C. for 1 hour and then heated to 180 ° C. for 4 hours. Measure the viscosity and the acid value of the contents in the kettle when heated to the same temperature and diluted to 67% with styrene until the viscosity is 4 to 5 seconds (25 ° C Gardner) and the acid value is 50 or less. After being heated and heated to 180 ° C., the viscosity was 4.5 seconds and the acid value was 19.5 after 4 hours. Cool to 160 ° C., increase the amount of nitrogen gas blown at the same temperature, and measure the viscosity and acid value in the same manner while removing the xylol for reflux. The viscosity is 6 to 9 seconds and the acid value is 40 or less. And After heating at 160 ℃,
It showed a viscosity of 7.8 seconds and an acid value of 18.6 in 1.5 hours. The number average molecular weight of this unsaturated polyester was 1,850 when measured by HLC (High Speed Liquid Chromatograph, Hitachi Chromatograph 635-0200, manufactured by Hitachi, Ltd., using polystyrene as a standard substance, the same applies hereinafter). After completion of the reaction, it was dissolved in styrene to which 0.2 part of hydroquinone was added with respect to 100 parts of styrene, and the heating residue was adjusted to 65% to obtain an unsaturated polyester resin composition. The composition had a viscosity of 8.2 seconds and an acid value of 18.5.

Example 2 In the same apparatus as in Example 1, diethylene glycol 457.
1 g (4.31 mol), ethylene glycol 267.3
g (4.31 mol), 406.1 g of phthalic anhydride (2.
74 mol), Versadim 216 228.1 g (0.
39 mol), 267 g (2.73 mol) of maleic anhydride, 0.2 g of hydroquinone and 40 g of refluxing xylol were charged and the temperature was raised from 150 ° C. to 180 ° C. in 4 hours, and the acid value of the contents in the kettle was kept at the same temperature. Was increased to 50 to 45, and the acid value became 48.4 in 6 hours after the temperature was raised to 180 ° C. Then cooled to 80 ° C. and maleic anhydride 194 g
(1.98 mol), allyl glycidyl ether 225.8
g (1.98 mol) and potassium benzoate (0.63 g) were charged, the temperature was kept at 90 ° C. for 1 hour, the temperature was raised to 180 ° C. for 4 hours, and the viscosity and the acid value were measured at the same temperature as in Example 1. While heating. The viscosity was 4. 5 hours after the temperature was raised to 180 ° C.
It showed 8 seconds and an acid value of 12.5. After cooling to 160 ° C. and heating at the same temperature for 2 hours while removing the reflux xylol in the same manner as in Example 1, the end point was reached when a viscosity of 7.6 seconds and an acid value of 10.9 was exhibited. The number average molecular weight of the unsaturated polyester was 1,730. After completion of the reaction, an unsaturated polyester resin composition was obtained in the same manner as in Example 1 with styrene added with 0.2 part of hydroquinone so as to be dissolved so that the heating residue became 65%. The composition had a viscosity of 8.1 seconds and an acid value of 9.
It was 9.

Example 3 Diethylene glycol 801.4 was placed in the same apparatus as in Example 1.
g (7.56 mol), tetrahydrophthalic anhydride 35
3.0 g (2.32 mol), Versadim 216 29
3.6 g (0.51 mol), fumaric acid 292.3 g
(2.52 mol), 0.2 g of hydroquinone and 40 g of xylol for reflux were charged, the temperature was raised from 150 ° C. to 190 ° C. in 5 hours, and the acid value of the contents in the kettle was 50 to 50 ° C. at the same temperature.
Heat to 45 and raise the acid value to 4 within 4 hours after heating at 190 ° C.
It became 5.3. Then, the mixture was cooled to 80 ° C., 144.7 g (0.95 mol) of tetrahydrophthalic anhydride, 107.7 g (0.95 mol) of allyl glycidyl ether and 0.3 g of potassium benzoate were charged, and the mixture was kept warm at 90 ° C. for 1 hour. The temperature was raised to 180 ° C. in 4 hours and heated at the same temperature as in Example 1 while measuring the viscosity and the acid value. 180
Seven hours after the temperature had risen, the viscosity was 4.2 seconds and the acid value was 12.5. The mixture was cooled to 160 ° C. and heated at the same temperature while removing xylene for reflux in the same manner as in Example 1. After heating for 2 hours, the end point was reached when the viscosity was 7.9 seconds and the acid value was 11.7. The number average molecular weight of the unsaturated polyester was 1,930. After completion of the reaction, hydroquinone 0.
An unsaturated polyester resin composition was obtained by dissolving 2 parts of styrene so that the heating residue was 65%. The composition had a viscosity of 8.1 seconds and an acid value of 11.6.

Comparative Example 1 Diethylene glycol 881.5 was placed in the same apparatus as in Example 1.
g (8.32 mol), 502.0 g of isophthalic acid (3.
(02 mol) was charged and the temperature was raised from 150 ° C to 220 ° C over 4 hours and heated at the same temperature until the acid value of the contents in the kettle reached 50 to 45. After heating at 220 ° C. and heating for 2.5 hours, the acid value became 47.1. Then, the mixture was cooled to 80 ° C., maleic anhydride 444.5 g (4.54 mol), allyl glycidyl ether 172.4 g (1.51 mol), potassium benzoate 0.48 g, hydroquinone 0.2 g and reflux xylol. 40 g was charged, the temperature was maintained at 90 ° C. for 1 hour, the temperature was raised to 180 ° C. in 4 hours, and heating was performed while measuring the viscosity and acid value of the contents in the kettle as in Example 1. After heating to 180 ° C., the viscosity was 4.2 seconds and the acid value was 25.3 within 3 hours.
After cooling to 160 ° C. and heating at the same temperature for 2 hours while removing the reflux xylol in the same manner as in Example 1, the end point was reached when a viscosity of 8.6 seconds and an acid value of 23.4 were exhibited. The number average molecular weight of the unsaturated polyester was 1,430. After completion of the reaction, an unsaturated polyester resin composition was obtained in the same manner as in Example 1 with styrene added with 0.2 part of hydroquinone so as to be dissolved so that the heating residue became 65%. The composition had a viscosity of 9.2 seconds and an acid value of 24.7.

Comparative Example 2 Diethylene glycol 951.4 was added to the same apparatus as in Example 1.
g (8.98 mol), 417.2 g of isophthalic acid (2.
51 moles) and 208.9 g of Versadim 216.
(0.36 mol) was charged and the temperature was raised from 150 ° C. to 220 ° C. over 4 hours and heated at the same temperature until the acid value of the contents in the kettle reached 50 to 45. After heating at the same temperature for 2 hours, it became 46.3. It is then cooled to 80 ° C. and maleic anhydride 42
2.2 g (4.21 mol), hydroquinone 0.2 g and xylol for reflux 40 g were charged, and the temperature was increased from 150 ° C. to 18
The temperature was raised to 0 ° C. in 3 hours. As in Example 1, the contents in the kettle were heated while measuring the viscosity and acid value. 180 ° C
After heating for 5 hours, the viscosity was 4.8 seconds and the acid value was 35.6. After cooling to 160 ° C. and heating at the same temperature for 1.5 hours while removing the reflux xylol as in Example 1, the viscosity was 9.6.
The second point was the end point when the acid value was 32.7. The number average molecular weight of the unsaturated polyester was 2,750. After completion of the reaction, an unsaturated polyester resin composition was obtained in the same manner as in Example 1 with styrene added with 0.2 part of hydroquinone so as to be dissolved so that the heating residue became 65%. The composition had a viscosity of 10.6 seconds and an acid value of 32.6.

Comparative Example 3 591.3 g of ethylene glycol was placed in the same apparatus as in Example 1.
(9.54 mol), phthalic anhydride 449.1 g (3.0
3 mol) and Versadim 216 252.3 g
(0.43 mol), maleic anhydride 339.8 g (3.
47 mol), 0.2 g of hydroquinone and 40 g of xylol for reflux were charged, the temperature was raised from 150 ° C. to 190 ° C. in 4 hours, and the contents were heated to the acid value of 50 to 45 at the same temperature. The acid value was 48. 5 hours after the temperature was raised to 190 ° C.
It became 5. Then, the mixture was cooled to 80 ° C., 170.0 g (1.74 mol) of maleic anhydride, 197.7 g (1.73 mol) of allyl glycidyl ether and 0.56 g of potassium benzoate were charged, and the mixture was kept warm at 90 ° C. for 1 hour. The temperature was raised to 180 ° C. in 4 hours and heated at the same temperature as in Example 1 while measuring the viscosity and the acid value. After heating to 180 ° C 5
It showed a viscosity of 4.2 seconds and an acid number of 12.1. 1
After cooling to 60 ° C. and heating for 1.5 hours at the same temperature while removing the reflux xylol as in Example 1, the viscosity was 7.8.
The second point was the end point when the acid value was 11.5. The number average molecular weight of the unsaturated polyester was 1,980. After completion of the reaction, an unsaturated polyester resin composition was obtained in the same manner as in Example 1 with styrene added with 0.2 part of hydroquinone so as to be dissolved so that the heating residue became 65%. The composition had a viscosity of 8.3 seconds and an acid value of 11.1.

Test Example The coating properties of the unsaturated polyester resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were tested as follows. (1) Formulation of putty paint The materials of the following formulations were sampled in 300 ml round cans, and stirred for 15 minutes with a high-speed dissolver to disperse them evenly.

[Table 1]

(2) Adjustment of test plate As a test plate, an iron plate (SPCC-S manufactured by Nippon Panel Co., Ltd.)
B), a zinc treated plate (manufactured by Nippon Panel Co., Ltd., SPG-C) and an electric zinc treated plate (manufactured by Nippon Steel Co., Ltd., Silver Alloy) were used to lightly polish the surface with water resistant paper # 150. (3) Preparation of test piece 2% of 55% methyl ethyl ketone peroxide was added to each paint prepared in (1), and putted on each test plate prepared in (2) to a thickness of 2 mm. (4) Measurement of coating film performance The following coating film performances of the putty paints obtained by using the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were tested, and the results are shown in Table 2.

(I) Drying property: After putty is put on an iron plate, the surface is lightly sanded with water-resistant paper # 150 with a finger at room temperature (20 ° C.) with time, and the time (minutes) when polishing is possible is measured. did. (Ii) Abrasiveness: After putty was put on an iron plate, left at room temperature (20 ° C.) for 4 hours, and then sanded with a finger using water-resistant paper # 50 to compare the easiness of sanding. evaluated. ◯: The putty coating film is often scraped off even with light polishing. Δ: The putty coating film is scraped off, but the polishing feels somewhat heavy. X: Heavy polishing, the putty coating film is not scraped well. (Iii) Adhesion: After putting putty on each test plate, at room temperature (20
℃) for 16 hours, then in a dryer at 120 ℃ 6
After baking for 0 minutes, the temperature was cooled to room temperature, and the putty adhesion of the bent portion when bent to a 90 ° angle from the center was examined and evaluated as follows. ○: Putty is attached. Δ: 50% putty is attached. X: No putty adhered.

(Iv) Moisture resistance: Putty was put on each of the above test plates, left at room temperature (20 ° C.) for 16 hours, and then the surface was polished with water-resistant paper # 240, # 150, and # 400 in this order. Was smoothed. Commercially available acrylic urethane paint (Isam paint, High Art) on a polished putty paint film
Spray coating (film thickness 40μ), 30 at room temperature (20 ℃)
After being left for minutes, it was dried for 60 minutes by a dryer at 60 ° C. After cooling, blister ring box (RH 99%, temperature 50
(° C) for 48 hours, and the state of the coating film surface (blister, foam having a diameter of about 2 mm) and the putty adhesion when bent to a 90 ° angle were examined. The blister was evaluated as follows, and the putty adhesion was evaluated by the same method as in (3). ○: No blister occurred. B: Blister is generated in 20% of the coating film. X: Blister is generated on the entire surface. (V) Heat cycle property: After putting putty on various test plates,
After being left at room temperature (20 ° C) for 16 hours, then heated in a dryer at 80 ° C for 2 hours, and immediately left in a freezer at -20 ° C for 2 hours, and this is repeated 4 times to obtain the external appearance (cracks) of the coating film. Was evaluated and evaluated as follows. ◯: No cracks occurred. Δ: 1 to 3 small cracks are included. X: Cracks are generated on the entire surface. From the results in Table 2, it is shown that the putty coating film using the resin composition of the present invention is excellent in drying property, polishing property, adhesion property, moisture resistance and heat cycle resistance.

[0030]

[Table 2]

[0031]

EFFECTS OF THE INVENTION The unsaturated polyester resin composition of the present invention is used for repairing automobiles, which is excellent in adhesion even to an electrogalvanized anticorrosive steel plate and is excellent in moisture resistance, drying property, polishing property and toughness. You can get putty paint.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shunji Masuda 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Factory

Claims (2)

[Claims] 1. A) (a) A, β-unsaturated polybasic acid and polybasic acid other than α, β-unsaturated polybasic acid are used in a molar ratio of 0.30 to 0.70: 0.70 to 0.30 (α,
β-unsaturated polybasic acid: α, a polybasic acid other than β-unsaturated polybasic acid), and in the polybasic acid other than the α, β-unsaturated polybasic acid, the dimer acid is the above α, a polybasic acid component included as a range of 0.01-0.10 in a molar ratio (0.70-0.30) of a polybasic acid other than the β-unsaturated polybasic acid,
(B) The molar ratio of ether glycol to glycol other than ether glycol is 1.00 to 0.30:
A glycol component having 0 to 0.70 (ether glycol: glycol other than ether glycol) and the formula (c): The allyl glycidyl ether represented by (a) :( b):
The molar ratio of (c) is 1.00: 1.50 to 0.70: 0.
The acid obtained by reacting the glycol component (b) and the allyl glycidyl ether (c) in an amount of 05 to 0.30 in an equimolar amount or more with respect to the polybasic acid component (a). Value 50 or less, number average molecular weight 500-1
30-80% by weight of unsaturated polyester of 50,000
And (B) an unsaturated polyester resin composition containing 20 to 70% by weight of a liquid polymerizable unsaturated compound. 2. A putty paint comprising the unsaturated polyester resin composition according to claim 1 as a binder.