JP4623357B2 - Unsaturated polyester resin composition and putty paint - Google Patents

Description

  The present invention relates to an unsaturated polyester resin, and more particularly to an unsaturated polyester resin composition suitable as a binder for automobile and vehicle repair putty and a putty coating using the same.

  In general, unsaturated polyester resins are relatively inexpensive compared to other resins, and are cured in a short time even at room temperature, providing excellent workability, and various excellent physical and chemical properties depending on the choice of main raw materials. For example, construction materials such as corrugated plates, bathtubs, septic tanks, industrial equipment such as tanks and pipes, transportation equipment such as ships and automobiles, electrical insulation materials, resin concrete, decorative boards, gel coats, putty paints, etc. Widely used.

  Automotive and vehicle repair putty paints are (1) quickly cured at room temperature (2) excellent in abrasiveness (3) excellent in adhesion to the base material (4) spatability Good (5) Performance such as no formation of burrows in the coating film is required.

  In particular, the spatability of (4) is an important factor for repair workability, and the burrow of (5) has an important effect on the durability of the coating film. The purpose is generally achieved by adding a leveling agent to the unsaturated polyester resin or putty, but all of these materials are expensive.

  The present invention solves the problems of the prior art, and is an unsaturated polyester resin composition that can be suitably used as a binder for automobiles and vehicle repair putty paints that are inexpensive and excellent in spatability and burrow generation. A putty paint using the same is provided.

  As a result of diligent research in view of the above problems, the present inventor has found that the combination of a polybasic acid component containing an α, β-unsaturated polybasic acid component with a certain amount or more and (B) provides spatability, In order to further improve the reduction of generation, a certain amount of hydroxyl-terminated 1,4 polybutadiene (B) and liquid are added to an unsaturated polyester (A) obtained by reacting a polyhydric alcohol component with a certain amount or more of an ether glycol component. The present inventors have found that the above object can be achieved by using an unsaturated polyester resin composition containing the polymerizable unsaturated compound (C) as a binder for putty paints, and have reached the present invention.

  That is, the present invention comprises (A) (a) a saturated polybasic acid and an α, β-unsaturated polybasic acid, and the use ratio thereof is 0 to 90: 100 to 10 mol% (saturated polybasic acid: α , Β-unsaturated polybasic acid) and (b) a polyhydric alcohol component in which 15 to 100 mol% of all polyhydric alcohol components have an ether bond, and the total number of polybasic acid components (a) The unsaturated polyester obtained by reacting the ratio of the total number of moles of the polyhydric alcohol component (b) with respect to the number in the range of 1.0 to 2.0, (B) 1,4-polybutadiene terminated with a hydroxyl group is unsaturated polyester (A ) 0.01 to 5.0% by weight with respect to 100 parts by weight, (A) and (B) total amount 30 to 80% by weight and (C) liquid polymerizable unsaturated compound 20 to 70% by weight. The present invention relates to an unsaturated polyester resin composition comprising, and a putty paint comprising this as a binder

The unsaturated polyester resin composition according to claim 1 can be suitably used as a binder for automobiles and vehicle repair putty paints having excellent spatability and reduction of coating hole formation.
The putty paint according to claim 2 is preferably suitable for automobiles and vehicle repairs having excellent spatability and reduced coating hole formation.

  Next, the best mode for carrying out the present invention will be described.

  The polybasic acid component (a) used in the present invention is composed of a saturated polybasic acid and an α, β-unsaturated polybasic acid, and the use ratio thereof is saturated polybasic acid: α, β-unsaturated polybasic Acid = 0 to 90: 100 to 10 mol%, preferably 0 to 60: 100 to 40 mol%. If the proportion of α, β-unsaturated polybasic acid used is outside the above range, curing at room temperature will be slow, and drying and polishing properties of the putty coating will be reduced.

  Examples of the saturated polybasic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, het acid, adipic acid, sebacic acid, and the like. Α, β-unsaturated polybasic acid For example, maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like are used. Two or more of each of the saturated polybasic acid and the α, β-unsaturated polybasic acid may be used in combination.

  As the polyhydric alcohol component used in the present invention, a polyhydric alcohol component having an ether bond in an amount of 15 to 100 mol%, preferably 50 to 100 mol%, is used.

  In order to investigate the relationship between the type of polyhydric alcohol component and the dryness and polishability of the putty coating when the component (C) is combined, diethylene glycol, which is a polyhydric alcohol having an ether glycol bond. , Dipropylene glycol, triethylene glycol, etc., and resin compositions obtained using these and resin compositions obtained from propylene glycol, neopentyl glycol, ethylene glycol, etc., which are polyhydric alcohols having no ether bond Observed. As a result, the former resin composition dried quickly and was excellent in abrasiveness, whereas the latter resin composition remained sticky on the coating film surface and was inferior in abrasiveness. This is presumed that the ether bond portion in the resin composition is excited by oxygen in the air and is oxidatively polymerizable. It was confirmed that the polyhydric alcohol having an ether bond in the polyhydric alcohol component needs to be used in an amount of 15 mol% or more. One or more polyhydric alcohol components having an ether bond and one or more polyhydric alcohol components having no ether bond may be used in combination.

  The unsaturated polyester (A) is obtained by a condensation reaction in which the ratio of the total number of moles of the component (b) to the total number of moles of the component (a) is in the range of 1.0 to 2.0. When the total number of moles of the component (b) is 1.0 or less, the acid value of the resin composition increases and the water resistance and alkali resistance of the putty coating film decrease. Further, when the total number of moles of the component (b) exceeds 2.0, the resulting resin composition has a low molecular weight, the curability at room temperature is lowered, and the putty coating film is softened at the same time, so that it is easy to be scratched during polishing work. .

  The unsaturated polyester (A) used in the present invention can be obtained by a conventional method. For example, the polybasic acid component and the polyhydric alcohol component are obtained by a condensation reaction at 100 to 230 ° C. in a nitrogen atmosphere.

  The molecular weight of the unsaturated polyester (A) is usually 500 to 10,000, preferably 800 to 5,000, from the workability of the putty paint, the drying property and water resistance of the coating film, and the acid value is usually 100 or less, preferably Prepared to 50 or less. In the present invention, an air-drying imparting material such as animal and vegetable oils or allyl compounds may be used within the allowable range.

  The number average molecular weight (measured according to ASTM D2503) of the hydroxyl-terminated 1,4 polybutadiene used in the present invention is preferably in the range of 1,000 to 10,000. In the structure of 1,4 polybutadiene, the 1,4-bond of the butadiene component is preferably 60 to 100 mol%, and the 1,2-bond is preferably 0 to 40 mol% in view of the effects of the present invention. When the hydroxyl group-terminated 1,4 polybutadiene is mixed with the unsaturated polyester resin, it may be diluted with a polymerizable monomer such as styrene monomer or methanol.

  These blending amounts are 0.1% of hydroxyl group-terminated 1,4 polybutadiene with respect to the total amount of unsaturated polyester and polymerizable monomer due to the spatability at the time of putty coating and the degree of occurrence of burrows in the putty coating. The range is from 01 to 5.0% by weight, preferably from 0.1 to 3.0% by weight, and more preferably from 0.07 to 2.0% by weight. If the amount is less than 0.01% by weight, the effect of removing bubbles cannot be obtained if the number of times of defoaming is reduced in the defoaming operation, and if it is more than 5.0% by weight, the curability is deteriorated.

The resin composition of the present invention contains 20 to 70% by weight of the above liquid polymerizable unsaturated compound (C) in a total amount of 30 to 80% of the unsaturated polyester (A) and 1,4-polybutadiene (B) having hydroxyl groups. To do.
When the blending ratio of the liquid polymerizable unsaturated compound (C) is less than 20% by weight, the reactivity is inferior, and a coating film having a high hardness cannot be obtained, and scratches are likely to occur during polishing of the putty coating film. On the other hand, if it exceeds 70% by weight, the putty coating will have poor durability and curability and adhesion will be reduced.

Examples of the liquid polymerizable unsaturated compound (C) used in the present invention include aromatic vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, t-butylstyrene, divinylbenzene, methyl acrylate, Methyl methacrylate, glycidyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate,
Examples include acrylic acid or methacrylic acid compounds such as 2-ethylhexyl acrylate. These may be used alone or in combination of two or more.

  When the resin composition of the present invention is used as a putty paint, a filler, a color pigment, a curing accelerator and the like are kneaded with a three-roll roll, a dissolver or the like, if necessary. Examples of the filler include talc, mica, kaolin, calcium carbonate, clay and the like. The filler is usually used in an amount of 30 to 80% by weight in the putty paint. Examples of the color pigment include titanium white, bengara, aniline black, carbon black, senior blue, manganese blue, iron black, chrome yellow, chrome green, and mapico yellow. The color pigment is usually used in an amount of 1 to 10% by weight in the putty paint. 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 the curing accelerator used is usually 0.1 to 10% by weight in the putty paint.

  In addition, a curing agent is mixed and dispersed at the time of painting (putting) in the paint. The curing agent is usually used in an amount of 1 to 4% by weight in the putty paint. As the curing agent, methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, or the like is used.

Hereinafter, the present invention will be described in detail with reference to examples. In the following examples, parts and% mean parts by weight and% by weight, respectively.
Example 1

<Manufacture of unsaturated polyester resin composition>
In a 2 liter four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a reflux condenser, 968.0 parts (9.13 mol) of diethylene glycol, 504.0 parts (3.32 mol) of tetrahydrophthalic anhydride, Maleic anhydride (524.0 parts, 5.35 mol) and hydroquinone (0.2 parts) were added, heated at 150 ° C. for 1 hour while blowing nitrogen gas, and then heated from 150 ° C. to 200 ° C. over 4 hours. The viscosity (Gardner, 25 ° C., the same applies hereinafter) and the acid value when diluted with styrene to a heating residue of 67% are measured and the viscosity is 8.8 seconds in 16 hours after heating at 200 ° C. The unsaturated polyester I was obtained with the end point of the acid value of 22.0 as the end point. After completion of the reaction, the reaction mixture was dissolved in styrene to which 0.1 part of hydroquinone was added, and adjusted so that the heating residue was 66%. To the unsaturated polyester resin, 0.1% of 1,4 polybutadiene having hydroxyl groups was added and stirred for 1 hour to dissolve uniformly. Thus, an unsaturated polyester resin I was obtained.
Similarly, 1.0% of hydroxyl group-terminated 1,4 polybutadiene was added to the unsaturated polyester resin, and the mixture was stirred for 1 hour and dissolved uniformly to obtain an unsaturated polyester resin II.
The unsaturated polyester resin has a viscosity of 7.9 seconds and an acid value of 21.3, and the molecular weight of the unsaturated polyester resin is 1,780 (HLC, high speed liquid chromatography, manufactured by Hitachi, Ltd., Hitachi chromatograph 635-0200). Polystyrene was used as a standard substance.
Comparative Example 1

  Unsaturated polyester I produced in Example 1 was synthesized, and after completion of the reaction, it was dissolved in styrene to which 0.1 part of hydroquinone was added, and adjusted so that the heating residue was 66% to obtain unsaturated polyester resin III. It was. To this unsaturated polyester resin III, 0.005% of 1,4 polybutadiene having a hydroxyl group was added, and stirred for 1 hour to dissolve uniformly to obtain unsaturated polyester resin IV.

（2）試験板の調製
試験板として鉄板（日本テストパネル社製、ＳＰＣＣ−ＳＢ）、亜鉛処理板（日本テストパネル社製、ＳＰＧ−Ｃ）および電気亜鉛処理板（新日鉄社製、シルバーアロイ）を用い、表面を耐水ペーパー＃150で軽く研磨した。
（3）試験片の作製
（1）で作製したそれぞれの塗料に55％メチルエチルケトンパーオキサイドを2％添加
し、これを（2）で調製した各試験板上に2ｍｍ厚にパテ付けした。
（4）塗膜性能の測定
実施例１および比較例１の樹脂組成物を用いて得たパテ塗料について下記に示す塗膜性能を試験し、その結果を表1に示した。
(a) 乾燥性：鉄板上へパテ付け後、常温（20℃）で経時ごとに表面を耐水ペーパー＃150を用いて指で軽く研磨し、研磨可能となる時間（分）を測定した。
(b) 研磨性：鉄板上へパテ付け後、常温（20℃）で4時間放置後、耐水ペーパー＃150を用いて指で研磨し、研磨のし易さを比較し、次のようにして評価した。
○：軽く研磨しても、よくパテ塗膜が削れる。
△：パテ塗膜が削れるが、研磨がやや重く感じる。
×：研磨が重く、パテ塗膜がよく削れない。
(c) 付着性：各試験板上へパテ付け後、常温（20℃）で16時間放置し、その後120℃
の乾燥機内で60分焼き付け後、常温まで冷却し、中央部より90°角に折り曲げた際の折り曲げ部のパテ付着性を調べ、次のようにして評価した。
○：パテが付着している。
△：50％パテが付着している。
×：パテの付着が見られない。
(d) ヘラ付け性：各種試験板上へパテ付け時のパテの塗布しやすさを評価した。
○：塗布作業時のパテの伸びがよく塗布しやすい。
×：塗布作業時のパテの伸びが悪く塗布しにくい。
（5）巣穴発生の有無：鉄板上へパテ付けし塗膜乾燥後、塗膜の巣穴の有無を確認した。 Test Example The coating properties of the unsaturated polyester resin compositions obtained in Example 1 and Comparative Example 1 were tested as follows.
(1) Putty paint blending Each of the following blending materials was collected in a 300 ml round can and stirred with a high-speed dissolver for 15 minutes to uniformly disperse.

(2) Preparation of test plate An iron plate (manufactured by Nippon Test Panel, SPCC-SB), a zinc-treated plate (manufactured by Nippon Test Panel, SPG-C) and an electrogalvanized plate (manufactured by Nippon Steel, Silver Alloy) The surface was lightly polished with water-resistant paper # 150.
(3) Preparation of test piece 2% of 55% methyl ethyl ketone peroxide was added to each coating material prepared in (1), and put 2 mm thick on each test plate prepared in (2).
(4) Measurement of coating film performance The following coating film performance was tested for putty paints obtained using the resin compositions of Example 1 and Comparative Example 1, and the results are shown in Table 1.
(a) Drying: After putting on an iron plate, the surface was lightly polished with a finger using water-resistant paper # 150 every time at room temperature (20 ° C.), and the time (minutes) at which polishing was possible was measured.
(b) Abrasiveness: Putty on iron plate, let stand at room temperature (20 ° C) for 4 hours, then polish with fingers using water-resistant paper # 150, compare the easiness of polishing, as follows evaluated.
○: Even when lightly polished, the putty coating is often shaved.
Δ: The putty coating is scraped, but the polishing feels somewhat heavy.
X: Polishing is heavy and the putty coating cannot be shaved well.
(c) Adhesiveness: putty on each test plate, let stand at room temperature (20 ℃) for 16 hours, then 120 ℃
After being baked in the dryer for 60 minutes, it was cooled to room temperature, and the putty adhesion of the folded part when it was folded at a 90 ° angle from the central part was examined and evaluated as follows.
○: Putty is attached.
Δ: 50% putty is attached.
X: Adherence of putty is not observed.
(d) Spatability: The ease of applying putty on various test plates was evaluated.
○: Elongation of putty during application work is good and easy to apply.
X: It is difficult to apply the putty because the putty does not grow well during the application.
(5) Presence / absence of burrows: Putty was put on an iron plate and the coating film was dried.

  From the results in Table 1, the resin composition of the present invention has low odor, and the putty coating using the resin composition is excellent in spatability and reduction of coating burrow generation. Indicated.

Claims (2)

(A) (a) It consists of a saturated polybasic acid and an α, β-unsaturated polybasic acid, and the use ratio is 0 to 90: 100 to 10 mol% (saturated polybasic acid: α, β-unsaturated polybasic acid A polybasic acid component which is a basic acid) and (b) a polyhydric alcohol component in which 15 to 100 mol% of all polyhydric alcohol components have an ether bond. The unsaturated polyester obtained by reacting the alcohol component (b) at a ratio of the total number of moles in the range of 1.0 to 2.0 and (B) hydroxyl group-terminated 1,4 polybutadiene is 0 to 100 parts by weight of the unsaturated polyester (A). Unsaturated polyester containing 0.01 to 5.0% by weight, comprising 30 to 80% by weight in total of (A) and (B) and (C) 20 to 70% by weight of liquid polymerizable unsaturated compound Resin composition. 2. A putty paint comprising the unsaturated polyester resin composition according to claim 1 as a binder.