JP3146688B2 - Unsaturated polyester resin composition and putty paint - Google Patents

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 automobile repair and a putty paint using the same.

[0002]

2. Description of the Related Art Generally, unsaturated polyester resins are relatively inexpensive as compared with other resins, and are hardened in a short time even at room temperature, so that they are excellent in workability. Due to its scientific properties, for example, construction materials such as corrugated sheets, bathtubs and septic tanks, industrial equipment such as tank containers and pipes, transportation equipment such as ships and automobiles, electrical insulating materials, resin concrete, decorative boards, gel coats, and putty paints Widely used for various applications.

In particular, putty paints for automobile repair include (1) excellent workability of spatula application, (2) quick curing at room temperature, (3) excellent abrasiveness, (4)
Excellent adhesion to the material, (5) Excellent adhesion to the topcoat, (6) Excellent moisture resistance, (7) Excellent durability (cracks). Performance is required.

However, in recent years, the material used for the outer wall of automobiles has been changed from an iron plate treated with zinc phosphate, iron phosphate or the like for the purpose of rust prevention to a metal plate mainly composed of zinc for the purpose of heavy corrosion protection. However, there has been a problem that, when repaired with a conventional putty, adhesion of the coating is hindered and peeling, blistering, etc. occur frequently. In addition, a method of improving the adhesion to the material by introducing dicyclopentadiene or a derivative thereof into unsaturated polyester has been carried out, but these unsaturated polyester resin compositions were used as binders for putty paints for automobile repair. Even in this case, adhesion to the electro-zinc-treated steel sheet is not sufficient, and peeling occurs.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, has excellent adhesion to an electro-zinc-treated rust-proof steel plate, and has abrasiveness, moisture resistance, durability and drying properties. It is intended to provide an unsaturated polyester resin composition which can be suitably used as a binder of an automobile repair putty paint having excellent heat resistance and a putty paint using the same.

[0006]

Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies and as a result, have found that polylactic acids containing at least a certain amount of α, β-unsaturated polybasic acid to accelerate curing at room temperature. Basic acid has a certain range of acid value to improve adhesion by chemical reaction with metals on the surface of the material, and a certain amount of ethylene oxide derivative of bisphenol A to further improve the adhesion to the material And / or a polyhydric alcohol containing a propylene oxide derivative of bisphenol A, and a certain amount of allyl glycidyl ether for improving the drying and polishing properties, are reacted at a constant blending ratio so as to have a constant molecular weight. The unsaturated polyester resin composition containing the unsaturated polyester (A) and the liquid polymerizable unsaturated compound (B) obtained by the above method as a putty binder. The present inventors have found that the above-mentioned object is achieved, and have reached the present invention.

That is, the present invention comprises (A) (a) a saturated polybasic acid and an α, β-unsaturated polybasic acid, and the use ratio thereof is 0 to 50: 100 to 50 mol% (saturated polybasic acid). :
polybasic acid (α, β-unsaturated polybasic acid), (b) 1 to 10 mol% of polyhydric alcohol in general formula (I)

Embedded image (Where n is an integer of 1 to 5)
And / or an ethylene oxide derivative of the general formula (I
I)

Embedded image (Wherein m is an integer of 1 to 5)
Polyhydric alcohol (c) which is a propylene oxide derivative of

Embedded image Allyl glycidyl ether represented by the following (a):
The molar ratio of (b) :( c) is 2.00 to 1.05: 1.0
0 to 0.50: 0.05 to 0.50, and the number of moles of the polybasic acid (a) is equimolar to the total number of moles of the polyhydric alcohol (b) and the allyl glycidyl ether (c) As described above, 30 to 80% by weight of an unsaturated polyester having an acid value of 40 to 70 and a number average molecular weight of 500 to 10,000 obtained by the reaction, and 20 to 70% by weight of a liquid polymerizable unsaturated compound (B). The present invention relates to an unsaturated polyester resin composition and a putty paint containing the unsaturated polyester resin composition as a binder.

The polybasic acid (a) used in the present invention comprises a saturated polybasic acid and an α, β-unsaturated polybasic acid. Basic acid = 0
~ 50: 100 ~ 50 mol%, preferably 0 ~ 30: 1
It is set to 00 to 70 mol%. When the use ratio of the α, β-unsaturated polybasic acid is out of the above range, the curing at room temperature becomes slow, and the dryness and abrasion of the putty coating film deteriorate.
As the above-mentioned saturated polybasic acid, for example, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hetic acid, adipic acid, sebacic acid and the like are used. As the α, β-unsaturated polybasic acid, for example, maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like are used. The above-mentioned saturated polybasic acids or α, β-unsaturated polybasic acids may be used in combination of two or more kinds.

The polyhydric alcohol (b) used in the present invention
Used is an ethylene oxide derivative and / or a propylene oxide derivative of bisphenol A represented by the general formula (I) or (II) in an amount of 1 to 10 mol%, preferably 1 to 6 mol% in a polyhydric alcohol. Is done.

The adhesion to the electro-zinc-treated steel sheet is improved by a material having excellent alkali resistance, such as an epoxy resin obtained from bisphenol A and epichlorohydrin, hydrogenated bisphenol A, etc. From the viewpoint of the balance of the overall properties of the putty coating film such as crack resistance, it is necessary to use the above derivative of bisphenol A as a part of the polyhydric alcohol. When the use ratio of the bisphenol A derivative is less than 1 mol% based on the total polyhydric alcohol, the adhesion to the electro-zinc-treated steel sheet decreases,
For example, when the putty coating film is baked at 120 ° C. for 30 minutes, the entire surface is peeled. Use of more than 10 mol% has no significant effect, and is economically disadvantageous.

Examples of the polyhydric alcohol component other than the ethylene oxide or propylene oxide derivative of bisphenol A include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butylene glycol, 2,3 -Butylene glycol, neopentyl glycol, 1,6-hexane glycol, trimethylolpropane, glycerin, trimethylolethane, pentaerythritol, water-added bisphenol A and the like are used. These may be used in combination. In particular, the use of diethylene glycol as the polyhydric alcohol is preferred from the viewpoint of the abrasiveness of the putty coating film.

In the present invention, allyl glycidyl ether (c) is used. Allyl glycidyl ether is excellent in reactivity, leaving no unreacted components and can be more completely introduced into the resin skeleton, thereby improving the adhesion to the zinc-treated steel sheet.

The unsaturated polyester (A) of the present invention is obtained by reacting a polybasic acid (a), a polyhydric alcohol (b) and an allyl glycidyl ether (c), and has an acid value of 40-7.
0, preferably 40-60 and a number average molecular weight of 500
It is adjusted so as to be 10,000 to 10,000, preferably 800 to 5,000. In order to adjust the acid value and the number average molecular weight to this range, the polybasic acid (a), the polyhydric alcohol (b) and the allyl glycidyl ether (c) are used in a molar ratio of (a) :( b) :( c). ) Is 2.00 to 1.05: 1.0
0 to 0.50: 0.05 to 0.50, preferably 1.5
0 to 1.05: 1.00 to 0.60: 0.05 to 0.4
With 0 mole, the number of moles of the polybasic acid (a) is at least equal to the number of moles of the total amount of the polyhydric alcohol (b) and the allyl glycidyl ether (c).

When the molar ratio of the polybasic acid (a) exceeds 2.00, the acid value of the unsaturated polyester (A) exceeds 70, so that the water resistance of the putty coating film is remarkably reduced. 1.0
If it is less than 5 (especially when the number of moles of (a) is less than the total number of moles of (b) and (c)), the unsaturated polyester (A)
Has an acid value of less than 40, and the adhesion to the zinc-treated plate is reduced. The higher the acid value of the unsaturated polyester (A), the better the adhesion to the zinc-treated plate. This is presumed to be due to the chemical bonding between the zinc ions of the material and the acid ions in the resin. However, the acid value of the unsaturated polyester (A) of the present invention is important because the acid value exceeding a certain value conversely lowers the water resistance and balances the adhesion and the water resistance. When the molar ratio of the polyhydric alcohol is less than 0.50, the number average molecular weight is less than 500, and the curability, crack resistance, chemical resistance and the like of the putty coating film are reduced. 1.0
If it exceeds 0, the acid value of the unsaturated polyester will be less than 40, and the adhesion to the material will be reduced. On the other hand, if the amount of allyl glycidyl ether used is less than 0.05, the dryness of the putty coating film is not sufficient, and the polishing property is significantly reduced. If it exceeds 0.50, the dryness is improved, but the putty coating is improved. The film becomes soft and the coating film is easily scratched during polishing.

When the acid value of the unsaturated polyester (A) of the present invention exceeds 70, the water resistance of the putty coating film decreases.
If it is less than 0, the adhesion to the zinc-treated steel sheet is reduced, and when the putty coating film is baked at 120 ° C. for 30 minutes, the entire surface is peeled. Further, when the number average molecular weight of the unsaturated polyester (A) is less than 500, the curing is not sufficient, and the polishing property of the putty coating film,
Water resistance decreases. In addition, the number average molecular weight is 10,000
If the amount exceeds the above range, the putty workability will decrease, and at the same time, the amount of the liquid polymerizable unsaturated compound (B) used will increase, and the meat retention will decrease.

The liquid polymerizable unsaturated compound (B) used in the present invention includes, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, t-butylstyrene, divinylbenzene, and acryl. Examples thereof include acrylic acid or methacrylic acid-based compounds such as methyl acrylate, methyl methacrylate, glycidyl methacrylate, and 2-ethylhexyl methacrylate. These may be used in combination.

The unsaturated polyester resin composition according to the present invention comprises 30 to 80% by weight of the above unsaturated polyester (A).
And the above-mentioned liquid polymerizable unsaturated compound (B) 20 to 7
Contains 0% by weight. If 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, and a high-hardness coating film cannot be obtained. In this case, the coating film is easily damaged. On the other hand, if it exceeds 70% by weight, the putty coating film has poor stickiness, and its curability and adhesion are reduced.

The unsaturated polyester (A) used in the present invention can be obtained by a conventional method. For example, the polybasic acid (a) and the polyhydric alcohol (b) are
C. and then a quaternary ammonium salt (for example, tetraammonium chloride, dimethyldodecylbenzylammonium chloride, etc.) or an alkali metal salt (for example, as a catalyst for ring-opening reaction of allyl glycidyl ether (c) and epoxy group). Potassium benzoate,
Sodium benzoate) in an amount of 0.05 to 5.0% by weight based on the allyl glycidyl ether;
It is obtained by performing a ring-opening addition reaction at 0 ° C.

When the resin composition of the present invention is used as a putty paint, a filler, a coloring pigment, a curing accelerator and the like are kneaded with a three-roll mill, a dissolver, and the like, if necessary. 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 coloring pigment include titanium white, red iron oxide, aniline black, carbon black, cyanine blue, manganese blue, iron black, chrome yellow, chrome green, and mapico yellow. The coloring pigment is usually used in the putty paint at 1 to 10% by weight. As a curing accelerator, for example, cobalt naphthenate, cobalt octenoate,
Examples 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. When applying the paint (putting on)
, 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 or the like is used.

[0020]

Embodiments of the present invention will be described below. In the examples, parts and% mean parts by weight and% by weight, respectively. Example 1 Diethylene glycol 7 was placed in a 2 liter four-necked flask equipped with a stirrer, gas inlet tube, thermometer and reflux condenser.
34.5 parts (6.93 mol), bisol 3PN (trade name, manufactured by Toho Chiba Chemical Industry Co., Ltd., propylene oxide derivative of bisphenol A, adduct of n = 3 in the above formula)
118.1 parts (0.30 mol), maleic anhydride 94
1.6 parts (9.6 mol), 0.2 parts of hydroquinone and 40 parts of xylene for reflux were charged, and heated at 150 ° C. for 1 hour while blowing nitrogen gas, and then heated at 150 ° C. to 190 ° C.
The temperature was raised in 4 hours until the acid value of the contents in the kettle became 14 at the same temperature.
Heated to 0-130. After heating at 190 ° C., the mixture was heated for 6 hours to reach an acid value of 135. Cool to 160 ° C., increase the amount of nitrogen gas blown, measure the acid value in the same manner at the same temperature while removing the xylene for reflux, until the acid value of the contents in the kettle becomes 110 to 120. Heated. 1.5 hours after heating at 160 ° C., the acid value became 116. Then 120
After cooling to 20 ° C., 205.4 parts (1.80 mol) of allyl glycidyl ether and 2.1 parts of dimethyldodecylbenzylammonium chloride as a ring-opening catalyst for allyl glycidyl ether were added, and the temperature was raised to 140 ° C. for 2 hours. The viscosity when diluted with styrene to 67% while heating at the same temperature and the acid value of the contents in the kettle were measured, and after heating at 140 ° C. for 6 hours,
Viscosity 7.8 seconds (Gardner, 25 ° C.) and acid value 58.6
Was indicated as the end point. The number average molecular weight of the unsaturated polyester is HLC (High Speed Liquid Chromatograph, manufactured by Hitachi, Ltd., Hitachi Chromatograph 635-020).
0, polystyrene was used as a standard substance, the same applies hereinafter), and found to be 2,830. After completion of the reaction, the resultant was dissolved in styrene to which 0.2 part of hydroquinone was added, and the content was adjusted so that the heating residue was 65% to obtain an unsaturated polyester resin composition. This composition had a viscosity of 7.6 seconds and an acid value of 38.
I got one.

Example 2 In the same apparatus as in Example 1, diethylene glycol 715.
4 parts (0.75 mol), bisol 3PN 115.0
Part (0.29 mol), 778.9 parts (7.95 mol) of maleic anhydride, tetrahydrophthalic anhydride 21
3.2 parts (1.40 mol), 0.2 part of hydroquinone and 40 parts of xylene for reflux were charged and heated at 150 ° C. for 1 hour as in Example 1, and then heated from 150 ° C. to 190 ° C.
The temperature rises at the same time and the acid value of the contents in the kettle is 130 to 12 at the same temperature.
Heated to zero. After heating at 190 ° C., the mixture was heated for 8 hours to obtain an acid value of 125. After cooling to 160 ° C. and increasing the amount of nitrogen gas blown in the same manner as in Example 1, removing the xylene for reflux and measuring the acid value in the same manner, the acid value of the contents in the kettle was 11%.
Heat until 5-100. After heating to 160 ° C, 2
The acid value reached 108 in hours. Then, the mixture was cooled to 120 ° C., and 180.2 parts of allyl glycidyl ether (1.58
Mol) and 1.8 parts of dimethyldodecylbenzylammonium chloride, and the mixture was heated to 140 ° C. for 2 hours.
While heating at the same temperature, the styrene dilution viscosity and the acid value of the contents in the kettle were measured in the same manner as in Example 1. After heating at 140 ° C. for 8 hours, the viscosity was 6.8 seconds and the acid value was 52.8. It was the end point at that time. The number average molecular weight of the unsaturated polyester was 1,890. After completion of the reaction, styrene containing 0.2 part of hydroquinone and heating residue of 6 parts were added in the same manner as in Example 1.
It melt | dissolved so that it might become 5%, and obtained the unsaturated polyester resin composition. The viscosity of this composition was 6.5 seconds, and the acid value was 34.3.

Example 3 In the same apparatus as in Example 1, diethylene glycol 702.
8 parts (6.63 mol), ethylene glycol 102.6
Part (1.66 mol), bisol 3PN 88.4 parts (0.22 mol), maleic anhydride 994.5 parts (1
0.15 mol), 0.2 part of hydroquinone and 40 parts of xylene for reflux were prepared, heated at 150 ° C. for 1 hour in the same manner as in Example 1, and then heated from 150 ° C. to 190 ° C. for 4 hours. It heated until the acid value of the content in a kettle became 100-95. The acid value became 98 in 7 hours after the temperature was raised at 190 ° C. Cool to 160 ° C., increase the amount of nitrogen gas blown in the same manner as in Example 1, measure the acid value in the same manner while removing the refluxing xylene, and the acid value of the contents in the kettle becomes 95 to 90. Until heated. 1.5 hours after heating at 160 ° C., the acid value reached 92. Then, the mixture was cooled to 120 ° C., and 110.5 parts (0.97 mol) of allyl glycidyl ether and 1.1 parts of dimethyldodecylbenzylammonium chloride were added.
The temperature was raised to 140 ° C. for 2 hours, and while heating at the same temperature, the styrene dilution viscosity and the acid value of the content in the kettle were measured in the same manner as in Example 1. After heating for 7.5 hours, the viscosity was changed to 8.6 seconds. The end point was reached when the acid value showed 48.6. The number average molecular weight of the unsaturated polyester was 3,120. After completion of the reaction, styrene to which 0.2 part of hydroquinone was added was dissolved in the same manner as in Example 1 so that the heating residue became 65%, to obtain an unsaturated polyester resin composition. The viscosity of this composition is 8.4
Seconds, the acid value was 31.6.

Comparative Example 1 Diethylene glycol 801.
0 (7.56 mol), 984.2 parts of maleic anhydride (1
0.04 mol), 0.2 part of hydroquinone and 40 parts of xylene for reflux were prepared, heated at 150 ° C. for 1 hour, heated to 190 ° C. in 4 hours, and heated at 190 ° C. in the same manner as in Example 1. Was heated until the acid value became 140 to 130.
After heating at 190 ° C., the mixture was heated for 7.5 hours to reach an acid value of 138.
Cool to 160 ° C., increase the amount of nitrogen gas blown, measure the acid value in the same manner at the same temperature while removing the xylene for reflux, until the acid value of the contents in the kettle becomes 110 to 120. Heated. After heating at 160 ° C., the acid value reached 118 in 1.5 hours. After cooling to 160 ° C. and increasing the amount of nitrogen gas blown to remove xylene for reflux, the acid value was measured in the same manner, and heating was performed until the acid value of the contents in the kettle became 110 to 100. After heating at 160 ° C. for 1.5 hours, the acid value became 103. Then, the mixture was cooled to 120 ° C. and charged with 214.7 parts (1.88 mol) of allyl glycidyl ether and 2.1 parts of dimethyldodecylbenzylammonium chloride.
Example 1 While heating to 0 ° C. for 2 hours and heating at the same temperature
The diluted viscosity of styrene and the acid value of the contents in the kettle were measured in the same manner as described above. After heating at 160 ° C. for 5 hours, the viscosity was determined to be 7.8 seconds and the acid value was 56.2. The number average molecular weight was 1,930. After completion of the reaction, hydroquinone 0.1.
The resulting mixture was dissolved in styrene to which 2 parts had been added so that the heating residue was 65% to obtain an unsaturated polyester resin composition. This resin composition had a viscosity of 7.5 seconds and an acid value of 36.5.

Comparative Example 2 In the same apparatus as in Example 1, diethylene glycol 940.
4 parts (8.87 mol), 869.7 parts (8.88 mol) of maleic anhydride, 0.2 part of hydroquinone and 40 parts of xylene for reflux were charged, and the same as in Example 1 at 150 ° C.
After heating for 1 hour from 150 ° C. to 190 ° C. in 4 hours, heating was performed at the same temperature until the acid value of the contents in the kettle became 50 to 40. 7 hours after the temperature was raised to 190 ° C, the acid value reached 46. After cooling to 160 ° C. and increasing the amount of nitrogen gas blown in the same manner as in Example 1, removing the xylene for reflux and measuring the acid value in the same manner, the acid value of the contents in the kettle was adjusted to 45 to 40. Heat until complete. The acid value became 43 by heating at 160 ° C. for 1 hour. Subsequently, the mixture was cooled to 120 ° C., and 214.7 parts (1.66 mol) of allyl glycidyl ether and 2.2 parts of dimethyldodecylbenzylammonium chloride were added.
The temperature was raised to 40 ° C. in 2 hours, and while heating at the same temperature, the styrene dilution viscosity and the acid value of the content in the kettle were measured in the same manner as in Example 1. After heating at 140 ° C. for 12 hours, the viscosity was 6.5 seconds. And when the acid value 8.2 was shown, it was set as the end point. The number average molecular weight was 1,570. After the completion of the reaction, styrene to which 0.2 part of hydroquinone was added was dissolved as in Example 1 so that the heating residue was 65% to obtain an unsaturated polyester resin composition. This composition had a viscosity of 6.3 seconds and an acid value of 3.3.

Comparative Example 3 Diethylene glycol 636.
0 parts (6.60 mol), 102.3 parts (0.26 mol) of bisol 3PN, 325.8 parts of maleic anhydride (3.
33 mol), 758.1 parts (4.99 mol) of tetrahydrophthalic anhydride, 0.2 part of hydroquinone and 40 parts of xylene for reflux were charged at 150 ° C. in the same manner as in Example 1.
After heating for 1 hour from 150 ° C. to 190 ° C. in 4 hours, heating was performed at the same temperature until the acid value of the contents in the kettle became 140 to 130. 10 hours after heating at 190 ° C, acid value is 13
It became 2. After cooling to 160 ° C. and increasing the amount of nitrogen gas blown in the same manner as in Example 1 and removing the xylene for reflux, the acid value was measured in the same manner.
Heated to 120. 1 hour by heating at 160 ° C for 2 hours
23. Then, the mixture was cooled to 120 ° C. and charged with 177.9 parts (1.56 mol) of allyl glycidyl ether and 1.8 parts of dimethyldodecylammonium chloride.
The temperature was raised to 140 ° C. in 2 hours, and while heating at the same temperature, the styrene dilution viscosity and the acid value of the contents in the kettle were measured in the same manner as in Example 1. After heating at 140 ° C. for 8 hours, the viscosity was 6.8 seconds. And an acid value of 53.4. The number average molecular weight is 1,860
Met. After the completion of the reaction, styrene to which 0.2 part of hydroquinone was added was dissolved as in Example 1 so that the heating residue was 65% to obtain an unsaturated polyester resin composition.
This composition had a viscosity of 6.4 seconds and an acid value of 34.7.

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) Putty paint composition Each of the following ingredients is collected in a 300 ml round can,
The mixture was stirred with a high-speed dissolver for 15 minutes to be uniformly dispersed.

[Table 1]

(2) Adjustment of test plate Iron plate (SPCC-S manufactured by Nippon Panel Co., Ltd.) was used as a test plate.
B), using a zinc-treated plate (Nippon Panel Co., SPG-C) and an electro-zinc-treated plate (Nippon Steel Co., Ltd., silver alloy), the surface was lightly polished with water-resistant paper # 150. (3) Preparation of Test Specimen 2% of 55% methyl ethyl ketone peroxide was added to each paint prepared in (1), and this was putty to a thickness of 2 mm on each test plate prepared in (2). (4) Measurement of coating film performance The coating film performance shown below was tested for putty paints obtained using the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3, and the results are shown in Table 1.

(I) Drying property: After putting on an iron plate, the surface is lightly polished with a finger using water-resistant paper No. 150 at room temperature (20 ° C.) at regular temperature (20 ° C.), and the time (minutes) at which polishing is possible is measured. did. (Ii) Abrasiveness: After putting on an iron plate, normal temperature (20 ° C)
For 4 hours, and then polished with a finger using water-resistant paper # 50. The easiness of polishing was compared and evaluated as follows. ：: The putty coating film is often shaved even if polished lightly. Δ: The putty coating film was shaved, but the polishing felt slightly heavy. X: The polishing is heavy, and the putty coating film cannot be removed well. (Iii) Adhesion: Putty on each test plate, then put at room temperature (2
(0 ° C.) for 16 hours, and then baked in a dryer at 120 ° C. for 60 minutes, cooled to room temperature, and examined the putty adhesion of the bent portion when bent at 90 ° from the center, as follows. Was evaluated. ：: Putty is adhered. Δ: 50% putty adhered. ×: No putty was observed.

(Iv) Moisture resistance: After putty on each of the above test plates, it was left at room temperature (20 ° C.) for 16 hours, and then the surface was polished with water-resistant paper # 240, # 150 and # 400 in order. Was smoothed. A commercially available acrylic urethane paint (made by Isaam Paint, Hi-Art) is spray-coated (film thickness: 40μ) on the polished putty coating film, left at room temperature (20 ° C) for 30 minutes, and then dried by a dryer at 60 ° C for 60 minutes. I let it. After cooling, a blistering box (RH 99%, temperature 50
C.) for 48 hours, and the state of the coating film surface (blister, foaming having a diameter of about 2 mm) and putty adhesion when bent at 90 ° were examined. The blister was evaluated as follows, and putty adhesion was performed in the same manner as in (3). ：: No blister was generated. Δ: 20% blister is generated in the coating film. ×: Blisters are generated on the entire surface. (V) Heat cycle property: After putting on various test plates,
After standing at room temperature (20 ° C.) for 16 hours, and then heating in a dryer at 80 ° C. for 2 hours, immediately standing in a freezer at −20 ° C. for 2 hours, and repeating this four times, the appearance of the coating film (crack) Was evaluated and evaluated as follows. ：: No crack occurred. Δ: 1 to 3 small cracks are present. ×: Cracks have occurred 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 dryness, abrasiveness, adhesion, moisture resistance and heat cycle resistance.

[0030]

[Table 2]

[0031]

According to the unsaturated polyester resin composition of the present invention, it has excellent adhesion to an electro-zinc-treated rust-proof steel sheet, and has excellent moisture resistance, drying properties, abrasiveness and toughness for automobile repair. Putty paint can be obtained.

(56) References JP-A-61-148266 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 C08L 67/06-67 / 07 C09D 167/06-167/07 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (A) (a) Consisting of (a) a saturated polybasic acid and an α, β-unsaturated polybasic acid, the ratio of which is 0 to 50: 1.
A polybasic acid which is 100 to 50 mol% (saturated polybasic acid: α, β-unsaturated polybasic acid);
10 mol% is represented by the general formula (I): (Where n is an integer of 1 to 5)
And / or an ethylene oxide derivative of the general formula (I
I) (Wherein m is an integer of 1 to 5)
Polyhydric alcohol (c) which is a propylene oxide derivative of Allyl glycidyl ether represented by the following (a):
The molar ratio of (b) :( c) is 2.00 to 1.05: 1.0
0 to 0.50: 0.05 to 0.50, and the number of moles of the polybasic acid (a) is equimolar to the total number of moles of the polyhydric alcohol (b) and the allyl glycidyl ether (c) As described above, 30 to 80% by weight of an unsaturated polyester having an acid value of 40 to 70 and a number average molecular weight of 500 to 10,000 obtained by the reaction, and 20 to 70% by weight of a liquid polymerizable unsaturated compound (B). An unsaturated polyester resin composition comprising: 2. A putty paint containing the unsaturated polyester resin composition according to claim 1 as a binder.