JPH06128365A - Unsaturated polyester resin composition and putty coating material - Google Patents

Abstract

PURPOSE:To obtain the title composition which can desirably be used as a binder which can give an automobile repair putty coating material excellent in polishability, moisture resistance and driability by mixing a specified unsaturated polyester with a liquid polymerizable unsaturated compound. CONSTITUTION:The composition comprises 30-80wt.% unsaturated polyester obtained by reacting a polybasic acid mixture comprising a saturated polybasic acid and an alpha,beta-unsaturated polybasic acid in a molar ratio of (0-50):(100-500 with a polyalcohol mixture containing 1-10mol%, based on the mixture, bisphenol A ethylene oxide derivative of formula I wherein n is an integer of 1-5 and/or a bisphenol A propylene oxide derivative of formula II wherein m is an integer of 1-5 and allyl glycidyl ether of formula III and having an acid value of 40-70 and a number-average molecular weight of 500-10000 and 20-70wt.% liquid polymerizable unsaturated 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 an automobile repair putty paint 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 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 boards, bathtubs, 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, putty paints Widely used for various purposes.

In particular, in the putty paint for automobile repair, (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) Etc. performance is required.

However, in recent years, a material used for the outer wall of an automobile is an iron plate treated with zinc phosphate, iron phosphate or the like for the purpose of rust prevention, and a metal mainly containing zinc for direct corrosion protection is directly applied to the iron plate. Since it has been transferred to the rust-proof steel plate which has been electrically treated, there is a problem that when repaired with a conventional putty, the adhesion of the coating is impeded, and peeling, blistering, etc. occur frequently. In addition, a method of introducing dicyclopentadiene or a derivative thereof into an unsaturated polyester to improve the adhesion to the material is used, but these unsaturated polyester resin compositions were used as a binder for a putty paint for automobile repair. Even in this case, the adhesion to the electrogalvanized 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 and has excellent adhesion to electrozinc treated rust-preventive steel sheets, and also has abrasiveness, moisture resistance, durability and dryness. The present invention provides an unsaturated polyester resin composition that can be suitably used as a binder for an automobile repair putty paint, and a putty paint using the same.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above problems, and as a result, as a result, a large amount of α, β-unsaturated polybasic acid containing a certain amount or more of α, β-unsaturated polybasic acid for accelerating the curing at room temperature was obtained. A certain amount of ethylene oxide derivative of bisphenol A which has a certain range of acid value for improving the adhesion of the basic acid by chemical reaction with the metal on the surface of the material and further improves the adhesion to the material. And / or a polyhydric alcohol containing a propylene oxide derivative of bisphenol A and a fixed amount of allyl glycidyl ether for improving the drying property and the polishing property are reacted at a fixed compounding ratio so as to have a constant molecular weight. By using the unsaturated polyester resin composition containing the unsaturated polyester (A) and the liquid polymerizable unsaturated compound (B) obtained as a binder of putty. The inventors have found that the above objects can be 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, the proportion of which is 0-50: 100-50 mol% (saturated polybasic acid). :
α, β-unsaturated polybasic acid), 1 to 10 mol% of the polyhydric alcohol in (b) polyhydric alcohol is the general formula (I).

[Chemical 4] Bisphenol A represented by the formula (n is an integer of 1 to 5)
Ethylene oxide derivative and / or the general formula (I
I)

[Chemical 5] (In the formula, m is an integer of 1 to 5) Bisphenol A
Alcohol (c) which is a propylene oxide derivative of

[Chemical 6] The allyl glycidyl ether represented by (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). 30-80% by weight of an unsaturated polyester having an acid value of 40-70 and a number average molecular weight of 500-10,000 and (B) a liquid polymerizable unsaturated compound of 20-70% by weight obtained as above. The present invention relates to an unsaturated polyester resin composition containing the same 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, the proportion of which is saturated polybasic acid: α, β-unsaturated polybasic acid. Basic acid = 0
˜50: 100 to 50 mol%, preferably 0 to 30: 1
It is set to 100 to 70 mol%. If the proportion of the α, β-unsaturated polybasic acid used is outside the above range, the curing at room temperature will be slow, and the dryness and polishability of the putty coating film will deteriorate.
Examples of the saturated polybasic acid include phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, het acid, adipic acid and sebacic acid. As the α, β-unsaturated polybasic acid, for example, maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc. are used. The saturated polybasic acid or the α, β-unsaturated polybasic acid may be used in combination of two or more kinds.

Polyhydric alcohol (b) used in the present invention
As the ethylene oxide derivative and / or propylene oxide derivative of bisphenol A represented by the general formula (I) or (II), 1 to 10 mol%, preferably 1 to 6 mol% in the polyhydric alcohol is used. To be done.

The adhesion to the electrogalvanized 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 characteristics of the putty coating film such as crack resistance, it is necessary to use the above-mentioned bisphenol A derivative as a part of the polyhydric alcohol. When the use ratio of the above-mentioned bisphenol A derivative is less than 1 mol% with respect to the total polyhydric alcohol, the adhesion property of the electrozinc treated steel sheet is lowered,
For example, when the putty coating film is baked at 120 ° C. for 30 minutes, peeling occurs on the entire surface. Further, even if it is used in an amount of more than 10 mol%, there is no remarkable effect, which is economically disadvantageous.

Examples of the polyhydric alcohol component other than the ethylene oxide or propylene oxide derivative of bisphenol A include, for example, 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. You may use these together. In particular, the use of diethylene glycol as the polyhydric alcohol is preferable from the viewpoint of the polishing property of the putty coating film.

In the present invention, allyl glycidyl ether (c) is used. Allyl glycidyl ether has excellent reactivity, and it is possible to more completely introduce it into the resin skeleton without leaving unreacted components, 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 to 7
0, preferably 40-60 and a number average molecular weight of 500
It is adjusted to be ~ 10,000, preferably 800-5,000. In order to adjust the acid value and the number average molecular weight within 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
0-1.05: 1.00-0.60: 0.05-0.4
As 0 mole, the number of moles of the polybasic acid (a) is equal to or more than 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, and the water resistance of the putty coating film remarkably deteriorates. Also 1.0
If it is less than 5 (particularly, if the number of moles of (a) is less than the total number of moles of (b) and (c)), the unsaturated polyester (A) will be adversely affected.
Has an acid value of less than 40, resulting in poor adhesion to the zinc-treated plate. The higher the acid value of the unsaturated polyester (A), the better the adhesion to the zinc-treated plate. It is presumed that this is because the zinc ions of the material and the acid ions in the resin are chemically bonded. However, when the acid value exceeds a certain level, the water resistance is decreased, and therefore the adhesion and water resistance are balanced, so that the acid value range of the unsaturated polyester (A) of the present invention is important. Further, 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 deteriorate. 1.0
If it exceeds 0, the acid value of the unsaturated polyester will be less than 40 and the adhesion to the raw material will decrease. On the other hand, when the amount of allyl glycidyl ether used is less than 0.05, the air-drying property of the putty film is not sufficient, and the polishing property is remarkably reduced. When it is more than 0.50, the air-drying property is improved, but the putty film is not applied. 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 is lowered, and 4
If it is less than 0, the adhesion to the zinc-treated steel sheet is lowered, and when the putty coating film is baked at 120 ° C. for 30 minutes, peeling occurs on the entire surface. Further, when the number average molecular weight of the unsaturated polyester (A) is less than 500, the curing is not sufficient, and the putty coating film has an abrasivity,
Water resistance is reduced. The number average molecular weight is 10,000.
If it exceeds the range, the putty workability is deteriorated, and at the same time, the amount of the liquid polymerizable unsaturated compound (B) used is increased, and the meat durability is deteriorated.

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 that time, the coating film is easily scratched. On the other hand, if the amount 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 (a) and the polyhydric alcohol (b) are added at 150 ° C to 220 ° C.
After polycondensation reaction at ℃, as a ring-opening reaction catalyst of allyl glycidyl ether (c) and epoxy group, quaternary ammonium salt (eg, tetraammonium chloride, dimethyldodecylbenzylammonium chloride, etc.) or alkali metal salt (eg, Potassium benzoate,
Sodium benzoate, etc.) is added in an amount of 0.05 to 5.0% by weight with respect to allyl glycidyl ether, and 80 ° C. to 18
It is obtained by carrying out a ring-opening addition reaction at 0 ° 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 7 was placed in a 2-liter four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a reflux condenser.
34.5 parts (6.93 mol), bisol 3PN (trade name of Toho Chiba Chemical 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, then from 150 ° C. to 190 ° C.
Up to 4 hours, and at the same temperature, the acid value of the contents in the kettle is 14
Heated to 0-130. After heating at 190 ° C., the mixture was heated for 6 hours to have an acid value of 135. Cool to 160 ° C., increase the amount of nitrogen gas blown in, 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. The acid value became 116 1.5 hours after heating at 160 ° C. Then 120
20.54 parts (1.80 mol) of allyl glycidyl ether and 2.1 parts of dimethyldodecylbenzylammonium choroid as a ring-opening catalyst for allyl glycidyl ether were added, and the temperature was raised to 140 ° C. in 2 hours. The viscosity when diluted to 67% with styrene 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).
It was 2,830 when polystyrene was used as a standard substance and the same was applied to the following). After completion of the reaction, it was dissolved in styrene to which 0.2 part of hydroquinone was added and adjusted so that the heating residue was 65% to obtain an unsaturated polyester resin composition. The composition has a viscosity of 7.6 seconds and an acid value of 38.
It was 1.

Example 2 In the same apparatus as in Example 1, diethylene glycol 715.
4 parts (0.75 mol), bis-ol 3PN 115.0
Parts (0.29 mol), maleic anhydride 778.9 parts (7.95 mol), tetrahydrophthalic anhydride 21
3.2 parts (1.40 mol), 0.2 parts of hydroquinone and 40 parts of xylene for reflux were charged and heated at 150 ° C. for 1 hour in the same manner as in Example 1, then from 150 ° C. to 190 ° C. 4
The temperature rises and the acid value of the contents in the kettle is 130 to 12 at the same temperature.
Heat to 0. After heating at 190 ° C., it was heated for 8 hours to have an acid value of 125. The mixture was cooled to 160 ° C., the amount of nitrogen gas blown in was increased in the same manner as in Example 1, and the acid value was measured in the same manner while removing xylene for reflux.
Heated to 5-100. After heating to 160 ° C, 2
The acid value reached 108 in time. Then, the mixture was cooled to 120 ° C. and 180.2 parts (1.58) of allyl glycidyl ether was added.
Mol) and 1.8 parts of dimethyldodecylbenzylammonium chloride, and heated to 140 ° C. for 2 hours,
While heating at the same temperature, the diluted viscosity of styrene and the acid value of the contents in the kettle were measured as in Example 1. After heating at 140 ° C. for 8 hours, a viscosity of 6.8 seconds and an acid value of 52.8 were exhibited. The time point was the end point. The number average molecular weight of the unsaturated polyester was 1,890. After completion of the reaction, styrene added with 0.2 part of hydroquinone was used in the same manner as in Example 1, and the heating residue was 6
It melt | dissolved so that it might become 5%, and obtained the unsaturated polyester resin composition. The composition had a viscosity of 6.5 seconds and an acid value of 34.3.

Example 3 In the same apparatus as in Example 1, diethylene glycol 702.
8 parts (6.63 mol), ethylene glycol 102.6
Parts (1.66 mol), bisol 3PN 88.4 parts (0.22 mol), maleic anhydride 994.5 parts (1
0.15 mol), 0.2 parts 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. for 4 hours at the same temperature. The contents in the kettle were heated until the acid value reached 100-95. An acid value of 98 was reached 7 hours after the temperature was raised to 190 ° C. The mixture was cooled to 160 ° C., the blowing amount of nitrogen gas was increased in the same manner as in Example 1, and the acid value was measured in the same manner while removing the refluxed xylene. The acid value of the contents in the kettle became 95 to 90. Heated up. An acid value of 92 was reached 1.5 hours after heating at 160 ° C. Then, the mixture was cooled to 120 ° C., 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, the styrene dilution viscosity and the acid value of the contents in the kettle were measured in the same manner as in Example 1 while heating at the same temperature, and after heating for 7.5 hours, the viscosity was 8.6 seconds and The end point was reached when the acid value was 48.6. The number average molecular weight of the unsaturated polyester was 3,120. After the reaction was completed, it was dissolved in styrene added with 0.2 part of hydroquinone 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.
The acid value was 31.6 seconds.

Comparative Example 1 In the same apparatus as in Example 1, diethylene glycol 801.
0 (7.56 mol), maleic anhydride 984.2 parts (1
0.04 mol), 0.2 parts of hydroquinone and 40 parts of xylene for reflux were charged, heated at 150 ° C. for 1 hour and heated to 190 ° C. for 4 hours in the same manner as in Example 1, and the contents in the kettle were kept at the same temperature. The acid value was heated to 140-130.
After heating at 190 ° C., the acid value became 138 by heating for 7.5 hours.
Cool to 160 ° C., increase the amount of nitrogen gas blown in, 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 became 118 in 1.5 hours. The mixture was cooled to 160 ° C., the amount of nitrogen gas blown in was increased, the xylene for reflux was removed, the acid value was measured in the same manner, and heating was performed until the acid value of the contents in the kettle reached 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.
The temperature was raised to 0 ° C. in 2 hours, and heating was performed at the same temperature as in Example 1.
The diluted viscosity of styrene and the acid value of the contents in the kettle were measured in the same manner as in 1., and after heating at 160 ° C. for 5 hours, the endpoint was reached when a viscosity of 7.8 seconds and an acid value of 56.2 were exhibited. The number average molecular weight was 1,930. After completion of the reaction, hydroquinone 0.
2 parts of styrene was added to the mixture to dissolve it so that the heating residue would be 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 Using 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 parts 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 at 150.degree. C., the temperature was raised from 150.degree. C. to 190.degree. C. in 4 hours, and the contents in the kettle were heated until the acid value became 50-40. The acid value became 46 7 hours after the temperature was raised to 190 ° C. The mixture was cooled to 160 ° C., the amount of nitrogen gas was increased in the same manner as in Example 1, and the acid value was measured in the same manner while removing the xylene for reflux, and the acid value of the contents in the kettle was adjusted to 45 to 40. Heated until. The acid value became 43 when heated at 160 ° C. for 1 hour. Then, the mixture was cooled to 120 ° C., 214.7 parts (1.66 mol) of allyl glycidyl ether and 2.2 parts of dimethyldodecylbenzylammonium chloride were added, and 1
The temperature was raised to 40 ° C in 2 hours, the styrene dilution viscosity and the acid value of the contents in the kettle were measured in the same manner as in Example 1 while heating at the same temperature, and after heating at 140 ° C for 12 hours, the viscosity was 6.5 seconds. And when the acid value was 8.2, it was set as the end point. The number average molecular weight was 1,570. After the reaction was completed, it was dissolved in styrene added with 0.2 part of hydroquinone in the same manner as in Example 1 so that the heating residue became 65% to obtain an unsaturated polyester resin composition. The composition had a viscosity of 6.3 seconds and an acid number of 3.3.

Comparative Example 3 With the same apparatus as in Example 1, diethylene glycol 636.
0 part (6.60 mol), bisol 3PN 102.3 parts (0.26 mol), maleic anhydride 325.8 parts (3.
33 mol), tetrahydrophthalic anhydride (758.1 parts) (4.99 mol), hydroquinone (0.2 parts) and refluxing xylene (40 parts) were charged, and the same procedure as in Example 1 was performed at 150 ° C.
After heating for 1 hour at 150.degree. C., the temperature was raised from 150.degree. C. to 190.degree. C. in 4 hours, and the contents in the kettle were heated until the acid value became 140 to 130. The acid value is 13 after 10 hours of heating at 190 ° C.
It became 2. The mixture was cooled to 160 ° C., the blowing amount of nitrogen gas was increased in the same manner as in Example 1, and the acid value was measured in the same manner while removing xylene for reflux.
Heat to 120. 1 by heating at 160 ℃ for 2 hours
23. Then, the mixture was cooled to 120 ° C., and 177.9 parts (1.56 mol) of allyl glycidyl ether and 1.8 parts of dimethyldodecyl ammonium chloride were added,
The temperature was raised to 140 ° C. in 2 hours, the styrene dilution viscosity and the acid value of the contents in the kettle were measured in the same manner as in Example 1 while heating at the same temperature, and after heating at 140 ° C. for 8 hours, the viscosity was 6.8 seconds. And an acid value of 53.4. Number average molecular weight is 1,860
Met. After the reaction was completed, it was dissolved in styrene added with 0.2 part of hydroquinone in the same manner as in Example 1 so that the heating residue became 65% to obtain an unsaturated polyester resin composition.
The composition had a viscosity of 6.4 seconds and an acid number 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 formulation Collect the materials of the following formulation into 300 ml round cans,
Stir with a high speed dissolver for 15 minutes to uniformly disperse.

[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 of the coating materials prepared in (1), and put on each test plate prepared in (2) in 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 1.

(I) Dryability: After putty was put on an iron plate, the surface was lightly sanded with water-resistant paper # 150 with a finger at room temperature (20 ° C.) with time, and the time (minutes) when polishing was possible was measured. did. (Ii) Polishing property: Putting putty on an iron plate and then at room temperature (20 ° C.)
After being left to stand for 4 hours at 4 ° C., water-resistant paper # 50 was used to polish with fingers, and the easiness of polishing was compared and evaluated as follows. ◯: 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 (2
0 ° C) for 16 hours, then bake in a dryer at 120 ° C for 60 minutes, cool to room temperature, and check the putty adhesion of the bent part when bent to a 90 ° angle from the center. Evaluated. ○: 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 in the order of water resistant papers # 240, # 150, and # 400 to obtain the surface. Was smoothed. A commercial acrylic urethane paint (Isam paint, Hiart) is spray-coated (film thickness 40μ) on the polished putty coating film, left at room temperature (20 ° C) for 30 minutes, and then dried in a dryer at 60 ° C for 60 minutes. Let 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. Δ: 20% blisters occur in 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.

Claims (2)

[Claims] 1. A composition comprising (A) (a) a saturated polybasic acid and an α, β-unsaturated polybasic acid, the proportion of which is 0 to 50: 1.
0 to 50 mol% (saturated polybasic acid: α, β-unsaturated polybasic acid), 1) in (b) polyhydric alcohol
10 mol% is represented by the general formula (I) Bisphenol A represented by the formula (n is an integer of 1 to 5)
Ethylene oxide derivative and / or the general formula (I
I) [Chemical formula 2] (In the formula, m is an integer of 1 to 5) Bisphenol A
Polyhydric alcohol (c) which is a propylene oxide derivative of The allyl glycidyl ether represented by (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). 30-80% by weight of an unsaturated polyester having an acid value of 40-70 and a number average molecular weight of 500-10,000 and (B) a liquid polymerizable unsaturated compound of 20-70% by weight obtained as above. An unsaturated polyester resin composition containing the same. 2. A putty paint comprising the unsaturated polyester resin composition according to claim 1 as a binder.