JPH03168244A - Unsaturated polyester resin composition and putty coating compound - Google Patents

Abstract

PURPOSE:To obtain a composition suitable for a binder of putty coating compound for repairing automobiles, having excellent adhesion to electrolytic zinc- coated carbon steel sheets, water vapor resistance, drying properties, etc., by adding a specific amount of a liquid polymerizable unsaturated compound to an unsaturated polyester prepared by reacting specific components. CONSTITUTION:(A) 30-80wt.% unsaturated polyester which is prepared by reacting A1: a polybasic acid component prepared by reacting 0-90mol% saturated polybasic acid (e.g. phthalic anhydride) with 100-10mol% alpha,beta-unsaturated polybasic acid (e.g. maleic anhydride) with A2: 2-50mol% polyhydric alcohol component composed of ethylene oxide derivative of bisphenol A shown by formula I (n is 1-5) and/or a propylene oxide derivative of bisphenol A shown by formula II (n is 1-5), A3: 3-30wt.% dicyclopentadiene and A4: 5-30wt.% allyl compound having >=40iodine value and/or air drying composition composed of animal or vegetable oil is blended with (B) 20-70wt.% liquid polymerizable unsaturated compound (e.g. styrene).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an unsaturated polyester resin composition, and more particularly to an unsaturated polyester resin composition suitable as a binder for putty paint for automobile refinishing and the use thereof. Regarding putty paint.

[Conventional technology]

In general, unsaturated polyester resins are relatively inexpensive compared to other resins, have excellent workability as they harden in a short time even at room temperature, and have various excellent physical and chemical properties depending on the selection of the main raw materials. Therefore, it can be used for various purposes such as 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 insulation materials, resin concrete, decorative boards, gel coats, and putty paints. Widely used.

In particular, putty paints for automobile repairs must (1) have excellent spatula workability, (2) quickly harden at room temperature, (3) have excellent abrasiveness, and (4) be compatible with the material. (5) Excellent adhesion with top coat paint; (6) Excellent moisture resistance; (7)
) Performance such as excellent durability (crack resistance) is required.

However, in recent years, the materials used for automobile exterior walls have changed from iron plates treated with zinc phosphate, iron phosphate, etc. for the purpose of rust prevention, to metals mainly containing zinc for heavy corrosion protection. Since there has been a transition to treated rust-proof steel sheets, when repaired with conventional putty, there was a problem that the adhesion of the film was inhibited and peeling, blasting, etc. occurred frequently.

In addition, dicyclobentadiene has been introduced into unsaturated polyester to improve its adhesion to materials, but even when these unsaturated polyester resin compositions are used as a binder for putty paints for automobile refinishing, electrical Adhesion to the zinc-treated mesh plate is not sufficient, and peeling occurs after baking at 120°C for about 20 minutes.

[Problems to be Solved by the Invention] It is an object of the present invention to solve the problems of the prior art described above, and to provide a material that has excellent adhesion to zinc-treated rust-proof steel sheets, and has excellent polishing properties, moisture resistance, durability, and drying properties. An object of the present invention is to provide an unsaturated polyester resin compound which can be suitably used as a binder for a putty paint for automobile repair, and a putty paint using the same.

[Means to solve the problem]

In view of the above-mentioned problems, the present inventors conducted intensive research and found that polybasic acids, α,β-monounsaturated polybasic acids, and polyhydric alcohol components containing more than a certain amount to accelerate curing at room temperature. A part of the material contains a bisphenol A derivative to reduce the effect of hardening inhibition caused by metals on the surface of the material and improve adhesion to electrogalvanized steel sheets, and a certain amount of bisphenol A derivative to improve adhesion to the material. An unsaturated polyester (A) obtained using dicyclobentadiene and a certain amount of air-drying agent to improve polishing properties, and a liquid polymerizable unsaturated compound (B).
) It has been discovered that the above object can be achieved by using an unsaturated polyester resin composition comprising the following as a binder for putty, and the present invention has been achieved based on this finding.

That is, the present invention provides (A) (a) a saturated polybasic acid and α. It consists of β-monounsaturated polybasic acid, and its usage ratio is 0.
~90: 100 to 10 mol% of the polybasic acid (saturated polybasic acid: α,β monounsaturated polybasic acid), (c) 2 to 50 mol% of the polyhydric alcohol component has the general formula ( (wherein, n is an integer of 1 to 5) and/or (wherein, n is an integer of 1 to 5).
of bisphenol A (n is an integer of 1 to 5)
Polyhydric alcohols which are derivatives of propylene oxide, (C) some (a), (b
), 3 to 30% by weight based on the total amount of (C) and (d)
of dicyclobentadiene and (d) or a portion of (a), (
Unsaturated polyester 30-30 obtained by reacting 5 to 30% by weight of an allyl compound with an iodine value of 40 or more and/or an air-drying ingredient consisting of an animal or vegetable oil based on the total amount of b), (C) and (d) 80% by weight, and (B) 20 to 70% by weight of a liquid polymerizable unsaturated compound. Contains putty paint.

The polybasic acid component (a) used in the present invention is a saturated polybasic acid and α. Consists of β-monounsaturated polybasic acid, the ratio of which is saturated polybasic acid: α, β-monounsaturated polybasic acid = 0 to 90:
100-10 mol%, preferably 5-40:95-60
It is mole%. The α, β drying properties and polishing properties are reduced.

As the saturated polybasic acid, for example, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, het's acid, adibic acid, sebacic acid, etc. are used. Further, as the α,β monounsaturated 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-monounsaturated polybasic acid may be used in combination.

Among these, maleic anhydride and fumaric acid are preferred as the α,β monounsaturated polybasic acids in order to facilitate the addition reaction of dicyclopentadiene (C).

The polyhydric alcohol component (b) used in the present invention contains 2 to 50 mol% of the ethylene oxide derivative and/or brobylene oxide derivative of bisphenol A represented by the above general formula based on the polyhydric alcohol component (b). be done.

Adhesion to electrogalvanized steel sheets can be improved by using materials with excellent alkali resistance, such as epoxy resins obtained from bisphenol A and epichlorostohydrin, hydrogenated bisphenol A, etc.; In order to balance the overall properties of the putty coating, it is necessary to use the bisphenol A derivative as a part of the polyhydric alcohol.

If the proportion of the bisphenol A derivative used is less than 2 mol % based on the total polyhydric alcohol component, the adhesion to the electrolytic galvanized steel sheet will decrease, for example, if the putty coating film is 120'
When baked for 30 minutes at C, peeling occurs on the entire surface. Moreover, even if it is used in an amount exceeding 50 mol %, there will be no significant effect and it will be economically disadvantageous.

Examples of polyhydric alcohols other than the ethylene oxide or propylene oxide derivatives of bisphenol 8 include ethylene glycol, brobylene glycol, diethylene glycol, triethylene glycol,
Dibrobylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, neobentyl glycol,! , 6-hexane glycol, trimethylolpropane, chrycerin, trimethylolethane, pentaerythritol, water-added bisphenol A, and the like.

These may be used in combination.

Dicyclopentadiene (C) used in the present invention is used in a proportion of 3 to 30% by weight, preferably 5 to 30% by weight based on the total amount of (a), (b), (C) and (d). be done.

Dicyclobentadiene is produced from the Cs distillate component of petroleum, and undergoes homopolymerization of itself by heating, Diels-Alder reaction to the double bond of α, β monounsaturated polybasic acid, and reaction with the carboxyl group of the polybasic acid. It takes many reaction forms such as addition reactions. By adding dicyclobentadiene, the adhesion to the electrogalvanized mesh plate can be further improved due to the synergistic effect with the above-mentioned component (b).

If the proportion of dicyclopentadiene used is less than 3% by weight, a sufficient additive effect will not be obtained, and the adhesion of the electrogalvanized steel sheet will decrease. Further, even if it is used in an amount exceeding 30% by weight, no significant additive effect on adhesion is obtained, and the drying properties of the putty coating film are reduced.

The air-drying component (d) used in the present invention has an iodine value of 4.
It consists of 0 or more allyl compounds and/or animal and vegetable oils, and the proportions used are (a), (b), (C) and (
5 to 30% by weight, preferably 7 to 2% by weight relative to the total amount of d)
It is 5% by weight.

If the air drying ratio is less than 5% by weight, the abrasiveness of the putty coating film will not be sufficient, and if it exceeds 30% by weight, the abrasiveness of the putty coating film will be good, but the hardness will not be sufficient. The paint film is easily scratched during polishing.

If the iodine value of the allyl compound or animal or vegetable oil is less than 40, the air drying properties of the putty coating will be poor, and sanding or bar polishing for smoothing the putty coating will not be possible, resulting in a significant decrease in workability.

When using allyl compounds and/or animal and vegetable oils, although allyl compounds have a greater effect on improving adhesion to electrogalvanized steel sheets than animal and vegetable oils, they tend to harden the putty coating and reduce polishing workability. Therefore, it can be determined appropriately from the viewpoint of the balance between these adhesion properties and polishing workability.

Examples of the allyl compound having an iodine value of 40 or more include allyl glycidyl ether, allyl glycol, glycerin monoallyl ether, glycerin diallyl ether, trimethylolbroban monoallyl ether, trimethylolpropane diallyl ether, pentaerythritol monoallyl ether, and pentaerythritol diallyl. Ether, pentaerythritol triallyl ether, etc. are used. Further, as the animal and vegetable oils having an iodine value of 40 or more, soybean oil, linseed oil, dehydrated castor oil, safflower oil, cottonseed oil, tung oil, fish oil, etc. are used. Also, transesterified oils or fatty acids of these oils can be used. It is preferable to use these allyl compounds and animal and vegetable oils together in terms of adhesion to steel plates and polishing workability of the putty. The unsaturated polyester (A) used in the present invention can be obtained by a conventional method. For example, the polybasic acid precept (
a), the above-mentioned polyhydric alcohol compound), dicyclobentadiene (C) and air-dry compound (d)'J150-220
Polycondensation reaction is carried out at °C, or the polybasic acid (
All or part of a) and the polyhydric alcohol component (b)
) and dicyclopentadiene (C) from 120 to 220
After precondensation reaction at °C, the polybasic acid component (a)
and the air-drying portion (d), and add 120 to 2
6° obtained by condensation reaction at 20°C
The molecular weight of the
, OOO, preferably i,ooo to 3,000, and its 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 aromatic vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, 1-butylstyrene, and divinylbenzene, methyl acrylate, Methyl methacrylate, glycidyl methacrylate,
Examples include methacrylic acid or acrylic acid compounds such as 2-ethylhexyl methacrylate. These may be used together. The unsaturated polyester resin composition of the present invention contains 30 to 80 weight percent of the unsaturated polyester (A) and 20 to 70 weight percent of the liquid polymerizable unsaturated compound (B). If the blending ratio of the liquid polymerizable unsaturated compound (B) is less than 20% by weight, the reaction with the unsaturated polyester (A) will not be sufficient, a coating film with high hardness will not be obtained, and the polishing of the putty coating film will be difficult. Extremely easy to get scratches. Moreover, if it exceeds 70% by weight, the properties of the putty coating film will deteriorate and the curability will decrease.

When using the resin composite bottom of the present invention as a putty paint,
If necessary, fillers, coloring pigments, and hardening accelerators are kneaded and blended using a three-roll, resolver, or the like. Examples of the filler include talc, mica, kaolin, calcium carbonate, and clay. Fillers are usually used in putty paints in an amount of 30-80% by weight. Examples of coloring pigments include titanium white, red iron oxide, aniline black, carpon black, cyanine blue, manganese blue &! ,
Examples include chrome yellow, chrome green, and mapico yellow. The coloring pigment is usually contained in the putty paint in an amount of 1 to 10
% by weight used. Examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octenoate, and manganese octenoate, and amines such as dimethylaniline and diethylaniline. The amount of curing accelerator used is usually 0.2 to 5% by weight in the putty paint.

Further, when applying the paint (putting), a hardening agent is mixed and dispersed. Hardeners are usually used in putty paints in an amount of 1 to 4% by weight. As the curing agent, methyl ethyl ketone peroxide, cyclohexanone peroxide, penzoyl peroxide, etc. are used. [Example] The present invention will be explained below with reference to Examples. Note that parts and % in the following examples mean parts by weight and % by weight, respectively.

Example 1 <Production of transesterified oil> Linseed oil (iodine value 170) was placed in a 2F four-necked flask equipped with a stirrer, gas inlet pipe, temperature system, and reflux condenser.
1.200 parts, 300 parts of glycerin and 0.5 parts of lead acetate
220 in 2 hours while blowing in nitrogen gas.
℃, and at the same temperature, the contents of the pot were heated to 1. The end point is the point when the state (25°C) becomes transparent when 1.5g of methanol is dissolved at 220'C.
It took 5 hours.

<Unsaturated polyester resin! II Production of bottom material> Using the same equipment as above, diethylene glycol 5 1 5.
2 parts (4.9 mol), Bisol 3PN (trade name, manufactured by Toho Chiba Chemical Industry Co., Ltd., adduct of bisphenol A with n=3 in the above formula of brobylene oxide), 216.0 parts (0.
54 mol), tetrahydrophthalic anhydride 1 3 3.
9 parts (0.88 mol), maleic anhydride 4 2 3.
4 parts (4.32 mol), dicyclopentadiene 1 8
0. Add 4 parts (10% by weight of the total amount charged) and 0.2 parts of hydroquinone, and blow in nitrogen gas.
After heating at 0°C for 1 hour, the temperature was raised from 140°C to 190°C in 3 hours, and at the same temperature the acid value of the contents in the pot reached 30-5.
It was heated until it reached 0. After raising the temperature to 190°C, the acid value reached 42.5 after heating for 3 hours.

Next, after cooling to 120″C, the transesterified oil 330,
5 parts (14.7 weight percent of the total amount as oil) and 40 parts of xylene were added, and the temperature was raised to 180"C.
Sampling was carried out over time at the same temperature, and the viscosity when diluted with styrene to a heating residue of 65% (Gardna, 25℃,
The same applies hereinafter) and acid value were measured. 5 after heating to 180″C
The viscosity was 3.5 seconds and the acid value was 28.

Next, the temperature was cooled to 160°C, and the amount of nitrogen gas injected was increased.
Similarly, while removing the xylene in the pot, add styrene to 65%.
The viscosity and acid value were measured when diluted to 160%.
After heating at 'C for 3 hours, the viscosity was 6.5 seconds and the acid value was 18.
The end point was the point where the test result was 2. After the reaction is completed, 0.0% of hydroquinone is added. It was dissolved in styrene to which 1 part was added, and the residue on heating was adjusted to 65% to obtain an unsaturated polyester resin composition.

The viscosity of this composition was 8.5 seconds, the acid value was 18, and the molecular weight of the unsaturated polyester was 1,800 (HLC: high speed liquid chromatography).

Example 2 Using the same equipment as in Example 1, ethylene glycol 30
8. 3 parts (4.97 mol), bisol 3PN35
1.0 parts (0.88 mol), tetrahydrophthalic anhydride 1'77.8 parts (1.17 mol), maleic anhydride 2
29.3 parts (2.34 mol), fumaric acid 271.4 parts (2.34 mol), dicyclopentadiene 126.4 parts (7.0% by weight of the total amount charged), and hydroquinone 0
．． 2 parts were added and heated in the same manner as in Example 1. After raising the temperature to 190°C and heating for 4 hours, the acid value was 35.3.

Next, after cooling to 100°C, the transesterified oil 170. 8 parts (7.0 parts of the total amount as oil)
6% by weight), allyl glycidyl ether (iodine value 22
2: 63.8 parts of M (9.1% by weight of the total amount charged), 98 parts (1 mol) of maleic anhydride, 1.061 parts of dimethyldodecylbenzylammonium chloride as a ring-opening catalyst for allyl glycidyl ether, and 40 parts of xylol were added. After heating at 120"C for 3 hours, the temperature was raised to 180 °C in 3 hours, and while heating at the same temperature, the viscosity and acid value were measured when diluted with styrene to a heating residue of 65% as in Example 1. It was measured.

The temperature was raised to 180°C, and 6 hours later, the viscosity was 3.6 seconds and the acid value was 2.5.

Next, it was cooled to 160"C, the amount of nitrogen gas injected was increased, and the viscosity and acid value when diluted to 65% with styrene were measured at the same temperature while removing xylene.
After heating for a period of time, the end point was a viscosity of 6.8 seconds and an acid value of 10.2. After the reaction was completed, it was dissolved in styrene to which 0.1 part of hydroquinone had been added so that the residue on heating was 65% to obtain an unsaturated polyester resin composite.

The viscosity of this composition was 7.9 seconds, the acid value was 9.8, and the molecular weight of the unsaturated polyester was 1.600 (HLC measurement).

Example 3 Using the same equipment as in Example 1, diethylene glycol 5
3 4. 2 parts (5.04 mol), bisol 3PN
2 2 4. Part O (0.56 mol), tetrahydride phthalic anhydride 1 2 7. 7 parts (0.84 mol), isophthalic acid 1 3 9. 4 parts (0.84 mol), adivic acid 81.8 parts (0.56 mol), maleic anhydride 3
2 9. 3 parts (3.36 mol), 160.0 parts of dicyclobentadiene (8.7% by weight of the total charge) and 0.0 parts of hydroquinone. 2 parts, heated at 140°C for 1 hour while blowing nitrogen gas, and then heated to 210"C in 4 hours.
and heated at the same temperature until the acid value reached 50 to 60.

After raising the temperature to 210'C, the acid value showed 54.2 in 2 hours. Next, it was cooled to 140'C, and 253 parts of trimethylolbrobane diallyl ether (iodine number 225, 13.7% by weight of the total amount charged) and 40 parts of xylene were added.
The temperature was raised to 180°C, and the viscosity and acid value were measured at the same temperature when diluted to 65% with styrene in the same manner as in Example 1.

The temperature was raised to 180℃, and after 7 hours the viscosity was 3.8 seconds and the acid value was 8.
．． 8 was shown.

Next, the temperature was cooled to 160°C, and the amount of nitrogen gas injected was increased.
6 with styrene at the same temperature while removing xylol.
The viscosity and acid value when diluted to 5% were measured, and after heating for 2.5 hours, the end point was a viscosity of 7.0 seconds and an acid value of 7.6. After the reaction is completed, 0.0% of hydroquinone is added. The mixture was dissolved in styrene to which 1 part was added so that the residue on heating was 65% to obtain an unsaturated polyester resin composition. The viscosity of this combination is 9.
8 seconds, the acid value was 7.2, and the molecular weight of the unsaturated polyester was 2,100 (HLC measurement).

Example 4 Using the same equipment as in Example 1, diethyl glycol 5 6
1. 4 parts (5.30 mol), bisol 3PN2
3 5. 4 parts (0.59 mol), tetrahydrophthalic anhydride 1 6 2. 6 parts (1.07 mol), maleic anhydride 3 6 7. 0 parts (3.75 mol), dicyclopentadiene iso. Part s (9.
3% by weight), 0.2 part of hydroquinone, 442.0 parts of linseed oil fatty acid (iodine value, 175) (22 parts of the total amount charged)
．． 7% by weight) and 40 parts of xylene were heated at 140°C for 1.5 hours while blowing nitrogen gas, and then heated to 180°C in 3 hours. The viscosity and acid value were measured when diluted to a heating residue of 65%. After heating at 180°C for 9 hours, it showed a viscosity of 3.2 seconds and an acid value of 16.8. Next, it was cooled to 160°C, the amount of nitrogen gas injected was increased, and while removing xylene, the viscosity and acid value were measured when diluted with styrene to a heating residue of 65%, and after heating for 3 hours, the viscosity was 65%. The final point was 0.8 seconds and an acid value of 15.2, and the mixture was dissolved in styrene to which 0.1 part of hydroquinone had been added so that the residue on heating was 65%, to obtain an unsaturated polyester resin composition. The viscosity of this powerful product was 8.8 seconds, the acid value was 14.8, and the molecular weight of the unsaturated polyester was 1,750 (HLC measurement). Comparative Example 1 Using the same equipment as in Example 1, diethylene glycol 4
7 7. 0 parts (4.5 moles), 1 ethylene glycol
8 6. 0 parts (3.0 mol), tetrahydrophthalic anhydride 2 2 8. 0 parts (1.5 mol), maleic anhydride 5 8 8. Add 0 part (6.0 mol) and 0.2 part of hydroquinone, and while blowing nitrogen gas, 1
The temperature was raised from 40'C to 190''C in 3 hours, and heated at the same temperature until the acid value reached 40 to 50.18
The acid value was 43.6 5 hours after raising the temperature to 0''C.

Next, after cooling to 120°C, the transesterified oil used in Example 1 3 4 3. 5 parts (15 parts of the total amount as oil)
．． 1% by weight) and 40 parts of xylene, l80″
C. At the same temperature, the viscosity and acid value were measured when the mixture was diluted with styrene to a heating residue of 65% in the same manner as in Example 1.

After raising the temperature to 180''C, it showed a viscosity of 3.6 seconds and an acid value of 18.5 after heating for 6 hours.

Next, it was cooled to 160°C, the amount of nitrogen gas injected was increased, and the remaining 65% of the heated residue was heated with styrene in the same manner while removing xylene.
The viscosity and acid value when diluted to 1% were measured, and after heating for 3 hours, the end point was a viscosity of 8.8 seconds and an acid value of 15.7. After the reaction is completed, 0.0% of hydroquinone is added. The mixture was dissolved in styrene to which 1 part was added so that the residue on heating was 65% to obtain an unsaturated polyester resin composition. The viscosity of 20 pairs is 10.7
The acid value was 15.0, and the molecular weight of the unsaturated polyester was 1,850 (HLC measurement).

Comparative Example 2 Using the same equipment as in Example 1, diethyl glycol 591
. 5 parts (5.58 mol), 248 parts of bisol 3PN (
0.62 mol), tetrahydride phthalic anhydride 1 5
3. 8 parts (1.01 mol), maleic anhydride 3 8
6. 1 part (3.94 moles) and 0.0 parts of hydroquinone.
2 parts, and while blowing nitrogen gas, raise the temperature from 140°C to 180°C in 4 hours, and at the same temperature, the acid value reached 35 ~
It was heated until the temperature reached 45. After raising the temperature to 180°C, the acid value showed 36.8 in 4 hours.

Next, after cooling to 100'C, the transesterified oil used in Example 1 189. 7 parts (8.3 weight f% of the total amount as oil), allyl glycidyl ether 152.
5 parts (8.4% by weight of total charge), 1 maleic anhydride
0 0. 0 part (1.02 mol), 0.5 part of dimethyldodecylbenzylammonium chloride as a ring-opening catalyst for allyl glycidyl ether, and 40 parts of xylol were heated at 120°C for 2 hours, and then heated to 180°C in 3 hours. Then, at the same temperature, the viscosity and acid value were measured when the mixture was diluted with styrene to a heating residue of 65% in the same manner as in Example 1.

After heating at 180°C for 6 hours, the viscosity was 3.7 seconds and the acid value was 1.
It showed 8.2.

Next, the temperature was cooled to 160°C, and the amount of nitrogen gas injected was increased.
While removing xylol, heat the residue 6 with styrene in the same way.
The viscosity and acid value when diluted to 5% were measured, and after heating for 3 hours, the end point was a viscosity of 7.8 seconds and an acid value of 16.2.

After the reaction was completed, it was dissolved in styrene to which 0.1 part of hydroquinone had been added so that the residue on heating was 65% to obtain an unsaturated polyester resin composition. The viscosity of this composite material was 8.0 seconds, the acid value was 15.9, and the molecular weight of the unsaturated polyester was 1,580 (HLC measurement).

Comparative Example 3 Using the same equipment as in Example 1, diethylene glycol 42
2.9 parts (3.99 mol), ethylene glycol 1 6
4. 9 parts (2.66 moles), 202.2 parts (1.33 moles) of tetrahydrophthalic anhydride, 1 7 parts of dicyclobentadiene 9. 6 parts (10.0% by weight of the total charge) and 0.0 parts of hydroquinone. After heating at 140°C for 1.5 hours while blowing nitrogen gas, the temperature was raised to 190°C in 3 hours, and heated at the same temperature until the acid value reached 30 to 40.19 After heating at 0'C for 2 hours, the acid value was 37.8.

The transesterified oil used in Example 1 was then cooled to 120'C. 6 parts (13 parts of the total amount as oil)
．． 4% by weight) and 40 parts of xylene at 180″C.
The viscosity and acid value were measured at the same temperature when the mixture was diluted with styrene to a heating residue of 65%.

Viscosity was 3.6 seconds and acid value was 8.8 after 7 hours of heating to 180℃.
showed that.

Next, the mixture was cooled to 160°C, the amount of nitrogen gas injected was increased, and the viscosity and acid value were measured when diluting the mixture to a heating residue of 65% while removing xylene. After heating for 3 hours, the end point was a viscosity of 6.2 seconds and an acid value of 7.2. After the reaction is complete,
Hydroquinone 0. It was dissolved in styrene to which 1 part was added so that the residue on heating was 65% to obtain an unsaturated polyester resin composition. The viscosity of this kumikaimono is 7.0 seconds, and the acid value is 6.
．． 8, and the molecular weight of the unsaturated polyester is 1,100
(HLC measurement).

<Test Example> The coating film properties of the unsaturated polyester resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were tested as follows.

(1) Putty paint formulation Materials with the following formulations were each collected in a 300 ml round can and stirred for 15 minutes using a high-speed dissolver to uniformly disperse them.

1 part unsaturated polyester resin 120.0 parts accelerator,
Diethylaniline 0. 2-part accelerator, 6% cobalt octenoate2. (1 styrene
6.0 parts Titanium white (manufactured by Fuji Titanium Co., Ltd.) 6.0 parts FS Le Lux 2 0 0. 03
3 4. Part 5 (2) Adjustment of test plate Iron plate as test plate (manufactured by Nippon Panel Co., Ltd., spcc-SB)
, a zinc-treated plate (SPGC manufactured by Nippon Panel Co., Ltd.) and an electrolytic zinc treatment 1 (Silver Alloy manufactured by Nippon Steel Corporation) were used, and the surface was lightly polished with waterproof paper #150.

(3) Preparation of test pieces 2% of 55% methyl ethyl ketone peroxide was added to each of the paints prepared in (1), and this was puttyed to a thickness of 21III1 on each test plate prepared in (2).

(4) Measurement of coating film performance The putty paints obtained using the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were tested for coating film performance as shown below, and the results are shown in Table I. .

(1) Drying After applying putty onto a two-iron plate, the surface was lightly polished with a finger using waterproof paper #150 over time, and the time (minutes) until polishing became possible was measured.

(2) Polishability: After applying putty on the iron plate, at room temperature (20℃)
After standing for a period of time, it was polished with fingers using waterproof paper #150, and the ease of polishing was compared and evaluated as follows.

O: Even with light polishing, the putty coating can be easily scraped off.

△: The burnt coating film can be scraped off, but the polishing feels a little heavy.

×: The polishing is heavy and the putty coating film cannot be removed well.

(3) Adhesion: After putting putty on each test plate, leave it at room temperature (20°C) for 16 hours, then bake it in a dryer at 12Q''C for 60 minutes, cool it to room temperature, and remove it from the center. 9
Putty adhesion (putty marks) when bent at a 0° angle was examined and evaluated as follows.

○: Putty marks are attached.

Δ: 50% putty traces adhered.

×: No putty residue observed.

(4) Moisture resistance: After applying putty on each test plate, at room temperature (20"
C) for 16 hours, then cover the surface with waterproof paper #2.
40, #150 and #400 to make the surface smooth. Spray a commercially available acrylic urethane paint (High Art manufactured by Isamu Paint Co., Ltd.) onto the polished putty film.
It was left at room temperature for 30 minutes and then dried in a dryer at 60"C for 60 minutes. After cooling, it was placed in a blistering box (RH 99%, temperature 50"C) for 48 hours to dry the coating surface. The state (blister) and putty adhesion (putty marks) when bent at a 90° angle were investigated. Blisters were evaluated as follows, and putty adhesion was evaluated in the same manner as in (3).

O: No blister occurred.

Δ: Pristar occurred on 20% of the coating surface.

×: Blisters are generated on the entire surface.

(5) Heat cycle property: After applying putty on various test plates,
Leave it at room temperature (20"C) for 16 hours, then heat it in a dryer at 80℃ for 2 hours, then immediately leave it in a -20℃ freezer for 2 hours. Repeat this 4 times to determine the external shape of the coating surface ( Cracks) were investigated and evaluated as follows.

O: No cracks were generated.

Δ: 1 to 3 small cracks are present.

×: Cracks are generated on the entire surface.

The results in Table 1 show that the putty coating film using the resin composition of the present invention has excellent drying properties, polishing properties, adhesion properties, moisture resistance, and heat cycle properties.

〔Effect of the invention〕

According to the unsaturated polyester resin composition of the present invention, it has excellent adhesion to electrogalvanized steel sheets, and has excellent moisture resistance, drying properties,
It is possible to obtain a putty paint for automobile repair with excellent abrasiveness and toughness.

Further, the unsaturated polyester resin composition of the present invention can also be used as a surfacer paint for woodworking or a UV curing paint by taking advantage of its adhesion, toughness, and air-drying properties.

Claims (1)

[Claims] 1. (A) (a) Consists of a saturated polybasic acid and an α,β-unsaturated polybasic acid, the ratio of which is used is 0 to 90:100 to 10
Polybasic acid component which is mol% (saturated polybasic acid: α,β-unsaturated polybasic acid), (b) 2 to 50 mol% of the polyhydric alcohol component has a general formula There is an ethylene oxide derivative of bisphenol A represented by ▼ (in the formula, n is an integer from 1 to 5) and/or ▲ formula,
There are chemical formulas, tables, etc. ▼ Polyhydric alcohol component which is a propylene oxide derivative of bisphenol A represented by (in the formula, n is an integer from 1 to 5) (c) Components (a), (b), (c) ) and (d) from 3 to 30% by weight, based on the total amount of dicyclopentadiene; and (d) from 5 to 30% by weight, based on the total amount of components (a), (b), (c) and (d). (B) 30 to 80% by weight of an unsaturated polyester obtained by reacting an air-drying component consisting of an allyl compound with an iodine value of 40 or more and/or an animal or vegetable oil, and (B) 20 to 70% by weight of a liquid polymerizable unsaturated compound. An unsaturated polyester resin composition containing. 2. A putty paint comprising the unsaturated polyester resin composition according to claim 1 as a binder.