JPH0578459A - Unsaturated polyester resin composition and putty coating material - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in adhesion to a zinc- treated anti-corrosive steel plate, polishability, moisture resistance, durability, etc., and suitable for a binder of a putty coating material for repair of an automobile by blending a polymerizable unsaturated liquid compound with a specified unsaturated polyester. CONSTITUTION:(A) A polybasic acid component composed of (i) a saturated polybasic acid (e.g. phthalic acid) and (ii) an alpha,beta-unsaturated polybasic acid (e.g. maleic acid) in (0-90):(100-10)mol% ratio of the component (i) to the component (ii) is reacted with (B) a polyalcohol component composed of (iii) a hydrogenated bisphenol A of formula I in an amount of 20-60wt.% based on the whole polyalcohol components and (iv) an allyl glycidyl ether of formula II in an amount of 10-40wt.% based on the whole polyalcohol components in 1-2 ratio of the total molar number of the component (A) to that of the component (B) to obtain an unsaturated polyester. With 30-80wt.% of the resultant unsaturated polyester, 20-70wt.% polymerizable unsaturated liquid compound (e.g. styrene) is blended, thus obtaining the objective composition.

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 in a short time even at room temperature. Due to its chemical 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, for putty paint for automobile repair, (1) excellent workability with a spatula, (2) quick curing at room temperature, (3) excellent polishability, (4) material Excellent adhesion with (5) excellent adhesion with topcoat paint, (6) excellent moisture resistance, (7) excellent durability (cracks), etc. Performance is required.

However, in recent years, the 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 sheet which has been electrically treated, there is a problem that when repaired with a conventional putty, the adhesion of the coating is inhibited and peeling, blistering and the like 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 is an automobile repair excellent in adhesion to a zinc-treated rust-preventive steel plate and excellent in polishing property, moisture resistance, durability and drying property. An unsaturated polyester resin composition that can be suitably used as a binder for 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, have found that a polybasic compound containing a certain amount or more of an α, β-unsaturated polybasic acid component for accelerating curing at room temperature. A certain amount of hydrogenated bisphenol A to improve the adhesion to the electrozinc treated steel sheet by reducing the effect of acid components and the inhibition of hardening by the metals on the surface of the material, and at the same time dry The unsaturated polyester (A) and the liquid polymerizable unsaturated compound (B) obtained by reacting a polyhydric alcohol component containing a fixed amount of allyl glycidyl ether with a fixed compounding ratio for improving the removability and the polishing property. The inventors have found that the above object can be achieved by using an unsaturated polyester resin composition containing the composition as a binder for putty, 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 to 90: 100 to 10 mol% (saturated polybasic acid : Α,
(β-unsaturated polybasic acid), and (b) 20 to 60 mol% of the total polyhydric alcohol component is represented by the general formula (I).

[Chemical 3] Hydrogenated bisphenol A represented by

[Chemical 4] The ratio of the total number of moles of polyhydric alcohol component (b) to the total number of moles of polybasic acid component (a) is 1.0 to 2.
An unsaturated polyester resin composition containing 30 to 80% by weight of an unsaturated polyester obtained by reacting as a range of 0 and (B) 20 to 70% by weight of a liquid polymerizable unsaturated compound, and this unsaturated polyester The present invention relates to a putty paint containing a resin composition as a binder.

The polybasic acid component (a) used in the present invention is
It is composed of saturated polybasic acid and α, β-unsaturated polybasic acid, and the ratio of its use is saturated polybasic acid: α, β-unsaturated polybasic acid =
0 to 90: 100 to 10 mol%, preferably 0 to 40:
It is 100 to 60 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. Examples of the α, β-unsaturated polybasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic acid,
Citraconic acid or the like is used. The saturated polybasic acid or the α, β-unsaturated polybasic acid may be used in combination of two or more kinds.

Polyhydric alcohol component used in the present invention
Examples of (b) include 20 to 60 mol% of hydrogenated bisphenol A represented by the general formula (I) based on the component, and 10
~ 40 mol% of allyl glycidyl ether of the formula (II) is used.

To prevent the adhesion of the putty coating film to the electrozinc treated plate, zinc metal is ionized, so that metal soap is formed by ionic bonding with a part of the components of the unsaturated polyester resin composition used as a binder. It is also presumed that it reacts with moisture in the air to form zinc hydroxide on the surface of the treated plate to hydrolyze a part of the unsaturated polyester resin composition. Therefore, it is necessary for the unsaturated polyester to have a resin structure that is excellent in alkali resistance and that does not leave unreacted components as much as possible. To improve alkali resistance, an epoxy resin obtained from bisphenol A and epichlorohydrin is used. When incorporated into the resin skeleton, it easily reacts with the polybasic acid component,
It becomes easy to gel. Therefore, by using hydrogenated bisphenol A having the same alkali resistance as the epoxy resin as the polyhydric alcohol component, it can be easily introduced into the resin skeleton.

Further, a drying oil and an allyl compound are used as a material for imparting drying property and polishing property to the putty coating film. In the former, unreacted components are likely to remain and are easily attacked by zinc ions. In the latter case, monoallyl ethers, diallyl ethers or triallyl ethers and glycidyl allyl ethers of glycerin, trimethylolpropane and pentaerythritol are generally used, but ether glycol components are unreacted components like oil components. Tend to remain and tend to be attacked by zinc ions. Of allyl compounds, allyl glycidyl ether is excellent in reactivity, no unreacted components remain, can be more completely introduced into the resin skeleton, and is excellent in adhesion to the zinc-treated steel sheet.

In the present invention, the polyhydric alcohol component is contained in an amount of 20 to 60 mol%, preferably 25, relative to the component.
By using ~ 50 mol% of hydrogenated bisphenol A and 10-40 mol%, preferably 15-35 mol% of allyl glycidyl ether, it is possible to prevent the formation of metallic soap by zinc ion and the hydrolysis by zinc hydroxide. Prevention,
Further, it is possible to improve the drying property and polishing property of the putty coating film.

When the amount of hydrogenated bisphenol A used is less than 20 mol% of the total polyhydric alcohol component, the adhesion to the electrozinc treated plate is lowered. For example, when the putty coating film is baked at 120 ° C. for 30 minutes. Complete peeling occurs, and 60 mol%
If it exceeds, the putty coating film becomes hard and polishing work becomes difficult. When the amount of allyl glycidyl ether used is less than 10 mol% in the total polyhydric alcohol component, the drying and polishing properties of the putty coating film are insufficient, and when it exceeds 40 mol%, the drying properties and polishing properties are good. However, the hardness is not sufficient, and the coating film is easily scratched during polishing.

As the polyhydric alcohol component other than the above,
For example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,
4-butylene glycol, neopentyl glycol,
1,6-hexanediol, trimethylolpropane,
Glycerin, trimethylolethane, pentaerythritol, ethylene or propylene adduct of bisphenol A, and the like are used. You may use these together. Further, as a component of the polyhydric alcohol having air-drying property, glycerin, trimethylolpropane and pentaerythritol monoallyl ether, diallyl ether or triallyl ether, the range which does not reduce the adhesion of the putty coating film to the electrozinc treated steel sheet, Specifically, it may be used in an amount of 2 mol% or less based on the total polyhydric alcohol.

The proportion of the polybasic acid component (a) and the polyhydric alcohol component (b) used is (b) based on the total number of moles of the component (a).
The ratio of the total number of moles of the components is 1.0 to 2.0, preferably 1.1 to 1.8. If the total molar ratio of the polyhydric alcohol component is less than 1.0, the acid value of the unsaturated polyester will not be sufficiently small, and the water resistance of the putty coating film will tend to decrease. On the other hand, if it exceeds 2.0, the molecular weight of the unsaturated polyester becomes small, and the curability of the putty coating film deteriorates, so that the drying property and the polishing property deteriorate, and at the same time, the adhesion property to the electrogalvanized steel plate also decreases.

The unsaturated polyester (A) used in the present invention can be obtained by a conventional method. For example, a quaternary ammonium salt (eg, tetraammonium chloride, dimethyldodecylbenzylammonium chloride, etc.) or an alkali metal salt (eg, potassium benzoate, benzoic acid) is used as a ring-opening reaction catalyst for the epoxy group of allyl glycidyl ether of the polyhydric alcohol component. Sodium etc.)
0.05 to 5.0 with respect to allyl glycidyl ether
% Of the polybasic acid component (a) is subjected to a pre-addition reaction with the polybasic acid component (a) at 80 to 140 ° C., and then the remaining polyhydric alcohol component and polybasic acid component are added,
Polycondensation reaction at 20 ° C. or the polybasic acid component
Part or all of (a) and the polyhydric alcohol component (b),
After polycondensation reaction at 150 to 220 ° C. with a polyhydric alcohol component excluding allyl glycidyl ether, allyl glycidyl ether and a ring-opening catalyst are added,
Obtained by polycondensation reaction at 220 ° C.

The molecular weight of the unsaturated polyester (A) depends on the workability of the putty paint, the water resistance and the adhesion of the coating film.
Usually 500 to 10,000, preferably 800 to 30,
The acid value is usually adjusted to 100 or less, more preferably 50 or less. Examples of the liquid polymerizable unsaturated compound (B) used in the present invention include styrene and α
-Methylstyrene, chlorostyrene, vinyltoluene,
Examples thereof include aromatic vinyl compounds such as t-butylstyrene and divinylbenzene, acrylic acid or methacrylic acid compounds such as methyl acrylate, 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 20 to 70% by weight of the liquid polymerizable unsaturated compound (B). When the compounding ratio of the liquid polymerizable unsaturated compound (B) is less than 20% by weight, the unsaturated polyester (A)
The reaction with is not sufficient, a coating film having a high hardness cannot be obtained, and the coating film is likely to be scratched during polishing of the putty coating film. Also, if it exceeds 70% by weight, the putty coating film becomes poor in meat holding property,
Curability and adhesion are reduced.

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 with a three-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 30 to 80% by weight in the putty paint. 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, mapico yellow and the like. The coloring pigment is usually used in the putty paint in an amount of 1 to 10% by weight. As a curing accelerator,
For example, metal soaps such as cobalt naphthenate, cobalt octenoate, and manganese octenoate, dimethylaniline,
Examples include amines such as diethylaniline. The amount of the curing accelerator used is usually 0.1 to 10% by weight in the putty paint. Further, a curing agent is mixed and dispersed at the time of applying the coating material (putting). 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 The present invention will be described in detail below with reference to examples. In the following examples, parts and% mean parts by weight and% by weight, respectively. <Production of Unsaturated Polyester Resin Composition> Example 1 Hydrogenated bisphenol A was placed in a 2-liter four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a reflux condenser.
(Shin Nippon Rika Co., Ltd., Ricabinol HB) 813.6 parts (3.39 mol), diethylene glycol 239.7 parts (2.26 mol), maleic anhydride 553.7 parts (5.
65 mol), 0.2 parts of hydroquinone and 40 parts of xylol for circulation, and 140 ° C. while blowing nitrogen gas.
After heating for 1 hour at 140 ° C., the temperature was raised from 190 ° C. to 190 ° C. over 3 hours, and the contents were heated at the same temperature until the acid value of the contents in the kettle reached 70-60. Acid value of 6 after heating at 190 ° C for 1.5 hours
It became 5.7.

Next, after cooling to 120 ° C., 193.2 parts (1.70 mol) of allyl glycidyl ether (Nippon Oil & Fats Co., Ltd. Epiol A) and dimethyldodecylbenzylammonium chloride as a ring-opening catalyst (Nippon Oil & Fats Co., cation) 3.86 parts of M2-100) were added, and the temperature was raised from 120 ° C to 175 ° C in 4 hours. Sampling was carried out at the same temperature every time, and the viscosity (Gardner, 25 ° C., the same applies hereinafter) and the acid value when diluted with styrene to a heating residue of 60% were measured, and the viscosity was raised 7 hours after the temperature was raised to 175 ° C. An acid value of 22 was shown for 5 seconds. Then, the mixture was cooled to 155 ° C., the nitrogen gas injection amount was increased, and the viscosity and acid value when similarly diluted to 60% with styrene were measured while removing the xylol in the kettle, and after heating at 160 ° C. for 2 hours The end point was when the viscosity was 6.3 seconds and the acid value was 15.2. After completion of the reaction, it was dissolved in styrene to which 0.1 part of hydroquinone was added, and the heating residue was adjusted to 60%. This composition has a viscosity of 7.1 seconds and an acid value of 15.0, and the unsaturated polyester has a molecular weight of 1,860 (HLC, high speed liquid chromatography, manufactured by Hitachi Ltd., Hitachi Chromatograph 635-0200, standard substance). Polystyrene was used for the above.

Example 2 Using the same equipment as in Example 1, ricabinol HB, 61
4.4 parts (2.56 mol), neopentyl glycol 3
99.4 parts (3.84 mol), maleic anhydride 627.
2 parts (6.40 mol), 0.2 parts of hydroquinone and 40 parts of xylol were added, the temperature was raised to 190 ° C. in the same manner as in Example 1, and the acid value after heating for 2 hours was 68.7. Next 12
Cool to 0 ° C., Epiol A, 145.9 parts (1.28
Mol) and cation M2-100, 2.92 parts were added, the temperature was raised to 175 ° C. in the same manner as in Example 1, and the viscosity and acid value were measured in the same manner. A viscosity of 3 hours after the temperature was raised to 175 ° C.
An acid value of 15.6 was shown for 3 seconds. Then, the mixture was cooled to 155 ° C. and the viscosity and acid value were measured in the same manner as in Example 1 while removing the xylol in the kettle.
After heating for an hour, the end point was reached when a viscosity of 6.8 seconds and an acid value of 11.7 were reached, and styrene was used to adjust the heating residue to 60%, as in Example 1. The viscosity of this composition was 7.9 seconds, the acid value was 11.2, and the molecular weight of the unsaturated polyester was 2,230.

Example 3 Ricabinol HB, 81 was prepared using the same apparatus as in Example 1.
5.0 parts (3.40 mol), neopentyl glycol 2
35.5 parts (2.26 mol), maleic anhydride 554.
7 parts (5.66 mol), 0.2 parts of hydroquinone and 40 parts of xylol were added, the temperature was raised to 190 ° C. in the same manner as in Example 1, and the acid value after heating for 1.5 hours was 62.6. Then cooled to 120 ° C., Epiol A, 193.6 parts (1.
70 mol) and 3.87 parts of cation M2-100 were added, the temperature was raised to 175 ° C. in the same manner as in Example 1, and the viscosity and acid value were measured in the same manner. 5.5 hours after the temperature was raised to 175 ° C., the viscosity was 4.0 seconds and the acid value was 12.8. Then, the mixture was cooled to 155 ° C., the viscosity and acid value were measured in the same manner as in Example 1 while removing the xylol in the kettle, and after heating at 155 ° C. for 2 hours, the viscosity was 7.6 seconds and the acid value was 9. At the time point when 8 was indicated, the end point was set, and as in Example 1, styrene was used and the heating residue was 60.
Adjusted to be%. The viscosity of this composition is 8.1.
The acid value was 9.6, and the molecular weight of the unsaturated polyester was 2,360.

Example 4 Ricabinol HB, 77 was prepared using the same equipment as in Example 1.
6.2 parts (3.23 mol), neopentyl glycol 2
24.2 parts (2.16 mol), tetrahydrophthalic anhydride 245.8 parts (1.62 mol), maleic anhydride 3
69.8 parts (3.77 mol), 0.2 parts of hydroquinone and 40 parts of xylol were added, and 19 parts were added in the same manner as in Example 1.
After heating to 0 ° C. and heating for 4 hours, an acid value of 61.6 was shown. Then cooled to 120 ° C., Epiol A, 184.3 parts (1.62 mol) and cation M2-100, 3.6.
Nine parts were added, the temperature was raised to 175 ° C. in the same manner as in Example 1, and the viscosity and acid value were measured in the same manner. 8.5 hours after the temperature was raised to 175 ° C., the viscosity was 3.6 seconds and the acid value was 18.9. Then 155
The mixture was cooled to 0 ° C. and the viscosity and acid value were measured in the same manner as in Example 1 while removing the xylol in the kettle. After heating at 155 ° C. for 4 hours, the viscosity was 6.6 seconds and the acid value was 15.6. The end point was reached at the indicated time, and the heating residue was adjusted to 60% with styrene as in Example 1. The viscosity of this composition was 7.2 seconds, the acid value was 15.1, and the molecular weight of the unsaturated polyester was 1,960.

Comparative Example 1 Using the same apparatus as in Example 1, diethylene glycol 3
10.9 parts (2.93 mol), neopentyl glycol 479.3 parts (4.61 mol), maleic anhydride 82
1.2 parts (8.38 mol), 0.2 parts of hydroquinone and 40 parts of xylol were added, and 190 parts were obtained in the same manner as in Example 1.
The temperature was raised to ℃ and after heating for 2 hours, an acid value of 60.9 was exhibited. Then, the mixture was cooled to 120 ° C., Epiol A, 191.1 parts (1.68 mol), and cation M2-100, 3.82 parts were added, and the temperature was raised to 175 ° C. in the same manner as in Example 1, and viscosity and acid were similarly set. The value was measured. 6.5 hours after the temperature was raised to 175 ° C., the viscosity was 3.0 seconds and the acid value was 11.6. Then, the mixture was cooled to 155 ° C., the viscosity and the acid value were measured in the same manner as in Example 1 while removing the xylol in the kettle, and after heating at 155 ° C. for 3 hours, the viscosity was 6.0 seconds and the acid value was 8. The end point was reached when 7 was reached, and the residue was heated with styrene in the same manner as in Example 1 to give a residue of 60.
Adjusted to be%. The viscosity of this composition is 6.5.
The acid value was 8.5, and the molecular weight of the unsaturated polyester was 2,750.

Comparative Example 2 Using the same apparatus as in Example 1, diethylene glycol 3
24.8 parts (3.06 mol), neopentyl glycol 478.0 parts (4.60 mol), maleic anhydride 75
0.7 parts (7.66 mol), trimethylolpropane diallyl ether (Osaka Soda, Neoallyl 20T) 2
45.9 parts (1.15 mol), 0.2 parts of hydroquinone and 40 parts of xylol were charged, heated at 140 ° C. for 1 hour while blowing nitrogen gas, and then heated from 140 ° C. to 180 ° C. in 3 hours, Sampling was performed at the same temperature every time, and the viscosity and the acid value were measured in the same manner as in Example 1 to obtain 180
The viscosity was 3.6 seconds and the acid value was 12.9 10 hours after the temperature was raised. Then, the mixture was cooled to 160 ° C., the viscosity and the acid value were measured in the same manner as in Example 1 while removing the xylol.
After heating at 160 ° C for 2 hours, viscosity 5.8 seconds and acid value 1
When 0.6 was reached, the end point was reached, and in the same manner as in Example 1, styrene was used to adjust the heating residue to 60%. The viscosity of this composition was 6.0 seconds, the acid value was 10.1, and the molecular weight of the unsaturated polyester was 2,690.

Comparative Example 3 Using the same apparatus as in Example 1, diethylene glycol 3
54.5 parts (3.34 mol), neopentyl glycol 521.7 parts (5.02 mol), maleic anhydride 64
8.0 parts (6.61 mol), linseed oil fatty acid (iodine number 170) 276.6 parts (0.99 mol), hydroquinone 0.2 part, dibutyltin oxide (ester reaction promoting catalyst) 0.5 part and Put 40 parts of xylol and heat at 150 ° C for 1 hour while blowing nitrogen gas, then 150 ° C
To 190 ° C. in 4 hours, sampling is performed at the same temperature over time, and the viscosity and the acid value are measured in the same manner as in Example 1. The viscosity is 3.6 seconds and the acid value is 18 at 190 ° C. in 12 hours. .6. Then, the mixture was cooled to 170 ° C., the viscosity and the acid value were measured in the same manner while removing the xylol as in Example 1, and after heating at 170 ° C. for 2 hours, the viscosity was 6.1.
When the second and the acid value were 15.2, the end point was reached, and styrene was adjusted in the same manner as in Example 1 so that the heating residue was 60%. The viscosity of this composition was 6.3 seconds, the acid value was 13.8, and the molecular weight of the unsaturated polyester was 2,480.

<Test Example> Examples 1 to 4 and Comparative Examples 1 to 1
The coating properties of the unsaturated polyester resin composition obtained in No. 3 were tested as follows. (1) Putty paint formulation The materials of the following formulation were sampled in 300 ml round cans and stirred for 15 minutes with a high-speed dissolver to disperse them evenly. Unsaturated polyester resin composition 120.0 parts Accelerator diethylaniline 0.2 parts Accelerator 6% Cobalt octenoate 2.0 parts Stabilizer 10% α-naphthoquinone styrene solution 0.3 parts Styrene 6.0 parts Titanium White (manufactured by Fuji Titanium) 6.0 parts FS Talc (manufactured by Nippon Talc) 200.0 parts ──────────────────────────── ───── 334.5 copies

(2) Adjustment of test plate An iron plate (SPCC-S manufactured by Nippon Panel Co., Ltd.) was used as a test plate.
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 performance was tested for putty paints obtained using the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3, and the results are shown in Table 1.

(1) Drying property: After putty was put on an iron plate, the surface was lightly sanded at room temperature (20 ° C.) with a finger using water-resistant paper # 150 every time, and the time (minutes) at which polishing was possible was measured. did. (2) Polishability: Putting putty on an iron plate and then 4 at room temperature (20 ° C)
After standing for a period of time, water-resistant paper # 150 was used to polish with fingers, and the ease 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: Polishing is heavy and the putty coating film cannot be scraped well. (3) Adhesion: After putting putty on each test plate, room temperature (20 ° C)
Left for 16 hours, 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 to a 90 ° angle from the center, and evaluated as follows. . ○: Putty is attached. Δ: 50% putty is attached. X: No adhesion of putty is observed.

(4) 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. A commercial acrylic urethane paint (Isam paint, Hiart) is spray-coated (film thickness 40μ) on the ground 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
Place in a blister ring box (RH 99%, temperature 50 ° C) for 48 hours, and then state of coating film surface (blister, diameter 2
(foaming of about mm) and putty adhesion when bent to 90 ° angle were examined. The blister was evaluated as described below, and the putty adhesion was evaluated by the same method as (3). ◯: No blister is generated. B: Blister is generated in 20% of the coating film. X: Blister is generated on the entire surface. (5) Heat cycle property: Putting putty on various test plates, left at room temperature (20 ° C) for 16 hours, then heated in a dryer at 80 ° C for 2 hours, then immediately left in a freezer at -20 ° C for 2 hours. Then, this was repeated 4 times to examine the external condition (cracks) of the coating film, and the evaluation was made as follows. ◯: No crack was generated. Δ: 1 to 3 small cracks are included. X: Cracks are generated on the entire surface.

[0032]

[Table 1] From the results in Table 1, 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.

[0033]

EFFECT OF THE INVENTION According to the unsaturated polyester resin composition of the present invention, a putty paint for automobile repair which is excellent in adhesion to an electrozinc treated plate and also excellent in moisture resistance, drying property, polishing property and toughness is obtained. be able to. Further, by utilizing the air-drying property, moisture resistance, adhesiveness and toughness of the unsaturated polyester resin composition of the present invention, it can be used as a surfacer coating material for woodworking, an FRP gel coating coating material, a UV curing coating material and the like.

Claims (2)

[Claims] 1. (A) (a) Consisting of a saturated polybasic acid and an α, β-unsaturated polybasic acid, the proportion of which is 0 to 90:10.
The polybasic acid component is 0 to 10 mol% (saturated polybasic acid: α, β-unsaturated polybasic acid), and (b) 20 to 60 mol% of all polyhydric alcohol components is represented by the general formula (I). [Chemical 1] Hydrogenated bisphenol A represented by the formula (10) to 40 mol% of the formula (II): The ratio of the total number of moles of polyhydric alcohol component (b) to the total number of moles of polybasic acid component (a) is 1.0 to 2.
An unsaturated polyester resin composition containing 30 to 80% by weight of an unsaturated polyester obtained by reacting as a range of 0 and (B) 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.