JPS6067515A - Topcoating compound composition - Google Patents

Abstract

PURPOSE:The titled composition having improved physical properties such as resistance to scratching, wax application resistance, etc., comprising a specific acrylic resin, oil-free polyester, and a crosslinking agent as binders. CONSTITUTION:The desired composition comprising (A) an acrylic resin obtained by copolymerizing 5-70wt% epsilon-caprolactone modified vinyl monomer shown by the formula (R is H, or CH3; n is 0.5-5) with 95-30wt% another radically copolymerizable unsaturated monomer, having 20-200 hydroxyl number, (B) an oil-free polyester having an acid component forming the polyester, comprising >=30mol% saturated aliphatic polybasic acid, and a composition with a range of the inside and the line of the tetragon obtained by connecting four points (0.8, 60), (0.8, 100), (1.00, 70), and (1.00, 100) when a ratio of dibasic acid in the polyester raw material is represented in the x-distance, and a mol% of >=3C glycol component in polyhydric alcohol in the y-distance, and (C) a crosslinking agent as binders.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a top coating composition, and more particularly to a top coating composition containing ε-
The present invention relates to a top coating composition having excellent physical properties such as scratch resistance and waxing resistance, which contains three components as binder components: an acrylic resin copolymerized with a caprolactone-modified vinyl monomer, an oil-free polyester, and a crosslinking agent.

In recent years, scratch resistance,
The requirements for waxing resistance are particularly increasing. Here, scratch resistance refers to the resistance to scratches caused by conventional hair fluttering and recent automatic car wash brushes, etc., and waxing resistance refers to the resistance to scratches caused by conventional brushing of hair and the brushes of recent automatic car wash machines. It refers to the property that when applied, the painted surface is less likely to get scratches or become dull, and the rag is less likely to become colored.

This waxing resistance is a performance required for coating films after being coated and also for coating films after being exposed outdoors.

Conventional alkyd resin-based topcoat paints and acrylic resin-based topcoat paints have poor scratch resistance and waxing resistance.
As seen in Japanese Patent No. 6-20068, the waxing resistance is excellent, but the scratch resistance is insufficient.

Therefore, the inventors of the present invention have developed
In addition to the conventional properties such as the weather resistance, water resistance, chemical resistance, mechanical properties of the paint film, adhesion to base coats, and adhesion of all 9 layers of the same paint, it also has especially scratch resistance, As a result of intensive research in order to obtain a top coat with excellent waxing resistance, we found that both scratch resistance and waxing resistance are due to the phenomenon of abrasion of the paint film, and that we have improved the coating film by making it more elastic. For example, in the case of acrylic resin topcoat paints, the glass transition temperature ('f'g
), or by using soft polybasic acids and soft polyhydric alcohols in the case of alkyd resin-based and oil-based polyether-based topcoats, but on the other hand, when the coated plates are stacked, the coating film is blocking or
However, there are disadvantages such as the coating film rapidly becoming hard at low temperatures and easily losing its elasticity, making it difficult to obtain a top coating that provides satisfactory performance.

As a result of further research into improving the abrasion resistance of paint films, the inventors found that acrylic resins copolymerized with ε-caprolactone-modified vinyl monomers The acrylic resin is an oil-free polyester resin that exhibits a remarkable effect on scratch resistance and waxing resistance, and also contains a certain amount or more of a saturated alicyclic polybasic acid as an acid component, and is relatively linear. The present inventors have discovered that a very useful top coating composition can be obtained that satisfies all of the above-mentioned properties, and has completed the present invention.

Thus, according to the present invention, (A) In the following general formula, R represents H or CH, and n is 0.5 to 5.
~70% by weight and other rajal copolymerizable unsaturated monomers 95%
(B) at least 3 of the acid components forming the polyester;
0 mole is a saturated alicyclic polybasic acid, and the horizontal axis is the value obtained by dividing the total number of moles of polybasic acid in the polyester raw material by the total number of moles of polyhydric alcohol (dibasic acid ratio). When the vertical axis is the molarity of glycol components with 3 or more carbon atoms in alcohol, (0, 8, 60), (0, 8, 100),
(i,oo.

70), an oil-free polyester consisting of a composition included on and inside a quadrilateral line surrounded by four points (1,00,100): and (C) a top coating composition containing a crosslinking agent as a binder. provided.

The acrylic resin (A) used in the present invention has the general formula CH2=CC00CH2CHzO(Co CHt CH
t CH2CHt CH20yaH In the formula, R is H or CH
ε-caprolactone modified vinyl monomer 5 to 5, where n is 0.5 to 5.
It is obtained by copolymerizing 70% by weight, preferably 10 to 50% by weight, with another radically copolymerizable unsaturated monomer.

The radically polymerizable unsaturated monomer to be copolymerized with the ε-caprolactone-modified vinyl monomer is limited to those having a radically polymerizable ethylenically unsaturated bond (>C==C). It is possible to select from a wide range of options depending on the desired performance of the acrylic resin as a final product.

Representative examples of such unsaturated monomers are as follows.

(a) Water curtain group-containing acrylic monomer: For example, cya hydroxyalkyl ester of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

(bl Esters of acrylic acid or methacrylic acid: e.g. methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, cyclohexyl acrylate, methacrylic acid Methyl, ethyl methacrylate, propyl methacrylate,
C1-6 alkyl or cycloalkyl esters of acrylic acid or methacrylic acid such as isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate: methoxybutyl acrylate, methoxybutyl methacrylate , methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate,
Alkoxyalkyl esters of acrylic acid or methacrylic acid, such as ethoxybutyl methacrylate. Grishijiruaku! J L/ -t or glycidyl methacrylate and C3
~, 8 monocarboxylic acid compounds (e.g. acetic acid, propionic acid, oleic acid, stearic acid, lauric acid, p-t-
butyl benzoic acid, etc.), and adducts of Cardura E-10 and unsaturated acids such as acrylic acid.

(cl Vinyl aromatic compounds: e.g. styrene, α-
Methylstyrene, vinyltoluene, p-chlorostyrene, vinylpyridine.

(d) α,β-ethylenically unsaturated carboxylic acids: for example acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, m-hydric maleic acid, fumaric acid.

9-(el Glycidyl group-containing vinyl monomer: for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether.

(n Amide of acrylic acid or methacrylic acid: e.g.
Acrylamide, N-methylolacrylamide, N-
Butoxymethylacrylamide.

(gl Ethylenically unsaturated monomers having alkoxysilane groups: e.g. γ-methacryloxytrimethoxysilane.

(hl Others: acrylonitrile, methacrylate trile.

These unsaturated monomers are appropriately selected depending on the desired physical properties, and may be used alone or in combination of two or more types and copolymerized with the ε-caprolactone-modified vinyl monomer.

The above copolymerization of the ε-caprolactone-modified vinyl monomer and the radically copolymerizable unsaturated monomer is known from JP-A No. 10-195714], for example, by using an acrylic copolymer. The production can be carried out using a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, etc. according to a method known per se. Advantageously, the polymerization is carried out according to a solution polymerization method, in which the two components mentioned above are generally combined in a suitable solvent in the presence of a polymerization catalyst, usually at about 0.
at a reaction temperature of from about 180°C, preferably from about 40 to about 170°C, for about 1 to about 20 hours, preferably from about 4 to about 1
This can be carried out by reacting for 0 hours.

Further, as the polymerization catalyst, it is possible to use conventional radical initiators for radical polymerization, such as azo compounds, peroxide compounds, sulfides, sulfines, diazo compounds, nitroso compounds, and redox compounds.

It is desirable that the acrylic resin copolymerized with 5 to 70% by weight of the 6-caprolactone modified vinyl monomer thus obtained has a hydroxyl value in the range of 20 to 2001, preferably 35 to 150.

In order to obtain the above-mentioned acrylic resin (A), during its preparation, the amounts of the ε-caprolactone-modified vinyl monomer and (if necessary) the hydroxyl group-containing acrylic monomer are adjusted so that the hydroxyl value has the above value. It is desirable to adjust the reaction conditions in advance so that the number average molecular weight falls within the above range.

The acrylic resin (A) used in the present invention has excellent scratch resistance, which is completely unexpected when used in a top coat.
It shows waxing resistance, but by itself,
It has disadvantages in terms of the finished appearance of the paint film (texture, smoothness), adhesion to undercoat, and adhesion when multiple coats of the same paint are applied. However, when this acrylic resin is used in combination with a specific oil-free polyester (B) described later, the performance of both acts synergistically to form a top coat that completely satisfies the above performance.

In the above-mentioned acrylic resin (A), if the amount of the ε-caprolactone modified monomer is less than 5% by weight, the resulting coating film will have poor elasticity, and excellent scratch resistance and waxing resistance will not be obtained. On the other hand, if the amount exceeds 70% by weight, the solubility in solvents and the compatibility with oil-free polyester and crosslinking agent decrease. Furthermore, if the hydroxyl value of the acrylic resin is less than 20, the reactivity with the crosslinking agent will decrease, and if it exceeds 200, the water resistance will decrease.

Oil-free polyester used in the present invention (
B) contains at least 30 of the total acid components as its acid component.
molti, preferably at least 40 molti of saturated alicyclic polybasic acid, and the value obtained by dividing the total number of moles of polybasic acid in the polyester raw material by the total number of moles of polyhydric alcohol (diacid ratio) When the horizontal 13-axis is the molarity of glycol components with 3 or more carbon atoms in the polyhydric alcohol, the vertical axis is (O, S.

60), (0,8,Zoo), (1,Oo,70), (
1,00,100), preferably (0,8,7
0), (0,8,90), (1,00,80), (1,
It is characteristic in that it consists of a composition contained on and within a quadrilateral line surrounded by four points (00, 100).

Among the acid components forming the oil-free polyester used in the present invention, examples of saturated alicyclic polybasic acids include:
Examples include hexahydrotetartaric acid and its anhydride, methylhexahydrophthalic acid and its anhydride, hexahydrotrimellitic acid and its anhydride, hexahydro-2-methyltrimellitic acid and its anhydride, and the like. Examples of other polybasic acids include phthalic acid and its anhydride, isophthalic acid and its dimethyl ester, te-14-phthalic acid and its dimethyl ester, trimellitic acid and its anhydride, 2-methyltrimellitic acid and its anhydride. aromatic polybasic acids such as pyromellitic acid and its anhydride;
Saturated dibasic acids represented by OC(CH,)nCOOH (n is an integer of 1 to 12); unsaturated polybasic acids such as tetrahydrophthalic anhydride and (anhydrous) maleic acid; and the like. When an unsaturated polybasic acid is used as part of the acid component,
For applications where weather resistance is important, the amount used should be limited to, for example, 10 mole or less, since the unsaturated bonds within the molecule impair the weather resistance of the coating film.

If the content of the saturated alicyclic polybasic acid in the acid component is less than 30 molti, the resulting oil-free polyester will have poor compatibility with the acrylic resin (A).

On the other hand, the polyhydric alcohol component of the oil-free polyester can be comprised of those conventionally commonly used in the formation of PolJ esters.

For example, glycol components include dihydric alcohols having 2 carbon atoms such as ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol,
1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1.4-butylene glycol, 1°5-bentanediol, 1,6-hexanedio-#, 2.5-hexanediol, Dihydric alcohols having 3 or more carbon atoms such as ester diol 204 (Union Carbide Co., Ltd. (USA) product), tricyclodecane dimetatool, 1,4-cyclohexanedimetatool, Examples include trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, cichentaerythritol, diglycerin, and sorbitol.

The oil-free polyester is produced by condensation polymerizing a saturated alicyclic polybasic acid with at least one alcohol as exemplified above in 1, along with an aromatic polybasic acid, a saturated dibasic acid, etc. as necessary, according to a conventional method. In particular, benzoic acid, p-t
-Butylbenzoic acid, benzoic acid methyl ester, etc. may be used to adjust the molecular weight. The reaction ratio between the polybasic acid component and the alcohol component is determined by the four points mentioned above, when the horizontal axis is the dibasic acid ratio and the vertical axis is the molarity of the glycol component with 3 or more carbon atoms in the polyhydric alcohol. Adjust so that it is included on the line and inside the enclosed quadrilateral.

An oil-free polyester obtained from a composition outside the above range has poor compatibility with the acrylic resin (A) used in combination with the oil-free polyester, and cannot be used for the purpose of the present invention.

The crosslinking agent (C) used in the present invention is a heat-curing type, as follows:
It is an aminoaldehyde resin and/or a blocked isocyanate, and a polyinsyanate is a type that can be cured at room temperature or by heating at a low temperature.

Aminoaldehyde resin contains melamine,
Urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, etc. are used, and most aminoaldehyde resins commonly used in paints can be used. Among them, melamine formaldehyde resin is most preferred from the viewpoint of weather resistance.

Block type polyisocyanates include tolylene diisocyanate, preferably non-yellowing polyisocyanates, such as isophorone diisocyanate, 18-hexamethylene diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and combinations thereof with water or polyhydric alcohols. The reactants are e.g. aliphatic or aromatic monoalcohol oximes,
Blocked polyisocyanates are made using commonly used blocking agents such as lactams and phenols, such as Tuffnate B-815N (Takeda Pharmaceutical Co., Ltd.).
product), Takune) B-84ON (Takeda Pharmaceutical Co., Ltd. product), Adrfuct B 1065 (Veba Ch
emie (Germany)), ADDITOL VXL-80 (
Hoechst Japan Co., Ltd. products) etc. When these block type polyisocyanates are used, a catalyst that promotes dissociation of the blocking agent is added as necessary.

As the polyisocyanate used for the room temperature or low temperature heating curing type, non-block forms of the above-mentioned blocked isocyanates can be used.

The acrylic resin used in the invention exhibits remarkable effects on pickpocket bath resistance and waxing resistance, and also on weather resistance, water resistance, and chemical resistance.

On the other hand, the oil-free polyester used in the present invention has excellent weather resistance, adhesion to undercoating and repeated coatings of the same paint,
Demonstrates excellent performance in terms of painted surface appearance.

That is, the top coating composition of the present invention exhibits scratch resistance and waxing resistance mainly due to the acrylic resin (A),
This lack of performance is compensated for by oil-free polyester (B), and the mixing ratio of these two types of resins and crosslinking agent (C) is determined by considering the role of each component, so that component (A) is 10% of the total binder. It is preferable that the component (B) is in the range of 5 to 50% by weight, and the outside weight (C) is in the range of 10 to 40M.

The top coating composition of the present invention may optionally contain a surface conditioner,
It is used by adding a curing accelerating catalyst, anti-cissing agent, ultraviolet absorber, antioxidant, quencher 1 and other additives.

The coating composition of the present invention thus obtained has scratch resistance,
In terms of performance such as waxing resistance, weather resistance, chemical resistance (acid resistance), ease of painting, appearance of the painted surface, flexibility, water resistance, and adhesion with base coats and overcoats. All of them are excellent and are suitable for solid color topcoating of car bodies.

Furthermore, recently, there has been a demand for high performance that cannot be applied with conventional coatings, such as the application of elastic coatings to bumper plastic elastic containers etc. using various organic elastomers such as automobile urethane. The composition can meet the above requirements due to its high elasticity, towability, adhesion to the base coat, etc.

In order to paint, for example, an automobile body using the coating composition of the present invention, first, the binder component consisting of an acrylic resin (A), an oil-free polyester (B), and a crosslinking agent (c), a commonly used coloring pigment, If necessary, add additives and make a paint using the usual method, and use a diluting solvent to reduce the paint viscosity to Ford Cup 44 (
20℃) for 20-30 seconds. Next, this is coated with an undercoat, if necessary, so that the coating material on which an intermediate coating film has been formed has an upwardly tilted dry film thickness of about 30 to 40 μm. Painting methods include regular air spray, airless spray, and electrostatic painting.

If the above coating composition is a heat-curing type using a yaminoaldehyde resin and/or a blocked isocyanate, it is left at room temperature for several minutes, then heated at 140 to 150°C for 20 to 40 minutes, and then cured at room temperature using a polyisocyanate. Or for low temperature curing type, if necessary, 20 to 6 at 40 to 80℃.
After heating for 0 minutes and standing for one day and night, the top coat 22- film which is the object of the present invention is obtained.

Hereinafter, the present invention will be explained in more detail with reference to Examples. Parts and weight percentages in the examples are by weight unless otherwise specified.
shows.

[I] Manufacture of varnish (1) Manufacture of acrylic resin varnish A In a normal acrylic resin varnish manufacturing apparatus equipped with a reaction tank, a stirrer, a monomer dropping tank, a heating and cooling device, etc., 40 parts of Kijiroll and 20 parts of butyl acetate were placed in the reaction tank. Prepare a portion and heat to 112°C.

This temperature (112°C) is maintained until the end of the reaction.

The monomer mixture described below is then added dropwise to the reaction vessel at a uniform rate over a period of 4 hours.

placel FM-3 Note-1) 40 parts 2-hydroxyethyl acrylate 10 Styrene 10
I n-butyl acrylate 39 parts Acrylic acid In 2.2'-azobisisobutyronitrile 1.21 notes
1) Product name: Manufactured by Daicel Chemical Industries, Ltd. ε-caprolactone modified vinyl monomer
0.5 part of '-azobisbutyronitrile is added in % portions over 1 hour at intervals of 10 minutes.

Then, after stirring was continued at 112° C. for 1 hour, the reaction was completed and the mixture was cooled. After cooling, 6.7 parts of Pheasant Roll was added to obtain acrylic resin varnish A with a solid content of 60%.

Acrylic resin varnish A had a hydroxyl value of 96.

(2) Production of acrylic resin varnish B Acrylic varnish B having the following monomer composition was prepared in the same manner as in the case of acrylic resin varnish A (however, the reaction temperature and the amount of 2.2'-azobisisobutyronitrile were different). Manufactured.

Placel FM-340 part 2-hydroxyethyl acrylate 61 styrene 3
01 n-butyl acrylate 231 Acrylic acid 11 The hydroxyl value of the resin component of acrylic resin varnish B was 77.

(3) Production of acrylic resin varnish C In the same manner as in the case of acrylic resin varnish A (however, the reaction temperature and the amount of 2.2'-azobisisobutyronitrile are different), acrylic resin varnish C having the following monomer composition is prepared. Manufactured.

2-hydroxyethyl acrylate 20 parts styrene
30I 25- n-Butyl acrylate 49 parts Acrylic acid 11 Acrylic resin varnish C had a hydroxyl value of 97.

This acrylic resin varnish C is used as a comparative example.

(4) Production of oil-free polyester varnish A Hexahydrophthalic anhydride 72.4 g parts (0.47 mol),
Phthalic anhydride 28.1 parts (0.19 mol), adipic acid 43.8 parts (0.3 mol), trimethylolpropane 3
2.8 parts (0.24 mol), neohentyl glycol 5
8.8 parts (0.56 mol) and 23.6 parts (0.20 mol) of 1,6-hexanediol were charged and heated. When the raw materials are melted and stirring becomes possible, stirring is started and the reaction tank temperature is raised to 240°C. However, from 160℃ to 24℃
The temperature was raised to 0°C at a uniform rate over 4 hours. The 26-condensed water produced is distilled out of the system through a rectification column. Once the temperature reaches 240°C, the temperature is kept constant and stirring is continued for 2 hours. Thereafter, pheasant was added to the reaction tank and the reaction was continued by switching to the solvent condensation method. When the acid value reaches 7, the reaction is terminated and the mixture is cooled. After cooling, 143 parts of Kijiroll was added to produce oil-free polyester varnish A having a solid content of 360%. The viscosity of this varnish is 2 (Gardner viscosity, 25°C
) The resin acid value was 7.1.

(5) Production of oil-free polyester varnish B Oil-free polyester varnish B'@:
Manufactured.

Isophthalic acid 106.2 parts (0.64 mol) Adipic acid 43.81/ (0.3 mol) Neopentyl glycol 85.31 (0.82 mol) Trimethylolpropane 24.11 (0.18 mol) obtained The solid content of oil-free polyester varnish B was 60%, and the viscosity was V (
Gardner viscosity (25° C.) and resin acid value were 6.9.

This oil-free polyester varnish B is used as a comparative example.

[■] Preparation of coating material (1) Steel sheet material: Apply cationic epoxy electrodeposition paint to a dull steel sheet treated with zinc phosphate to a dry film thickness of 20μ using the electrodeposition method and bake at 170℃ for 20 minutes. .

Next, after polishing the painted surface with 400 sandpaper, wipe the painted surface with gauze soaked in petroleum benzene to degrease it.

Thereafter, an amino alkyd intermediate paint for automobiles was applied to give a dry film thickness of 30 μm, and baked at 140° C. for 30 minutes.

Then, the coated surface was sanded with water using a $400 sand vapor, drained and dried, and the coated surface was wiped with petroleum benzene to prepare coated materials for examples of the present invention and for comparison.

(2) Glue for flexible material car bumpers Active injection mold A 3℃m thick plate of polyurethane resin is degreased with trichloroethane, and then a volatilized polyurethane resin primer is applied on top to a dry film thickness of approximately 10 microns. The coated material was used as a coating material.

Example 1 A blue multi-use paint was prepared using acrylic resin A by dispersion in a pebble ball mill with the following formulation.

60q6 Acrylic resin varnish A 66.7 parts 60 Thioyl-free polyester varnish A50 160q6 Upan 208E (Note-2) 50# Heliogen Blu
e 7040 (Note-3) 10 I (Note-2) Manufactured by Mitsui Toatsu Chemical Co., Ltd. Melamine resin 29- (Note-3) Manufactured by BASF West Germany Co., Ltd. Copper phthalocyanine pigment Pigment dispersion is made by adding an appropriate amount of Kijiroru to acrylic resin varnish. This was done using A. 40 ppm of silicone oil KP-322 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the paint as a coating surface conditioner.

The obtained paint was coated with Swazolna 1500 (Maruzen Oil Co., Ltd.).
(petroleum-based solvent)/kijirole/butylacetate, TI//n-
It was diluted with a mixed solvent of butanol = 30/20/30/20 to a viscosity of 26 seconds (Ford cup +4/20°C).

Air spray the diluted paint onto the surface of the painted material prepared in advance to a dry film thickness of 35 μm, let it set for 10 minutes at room temperature, and dry it in a hot air electric dryer at 140°C x 30°C.
Bake for a minute.

The test results of the obtained coated plates are shown in Table 2.

The pigment dispersion method, the addition of a coating surface conditioner, the method of preparing a test coated plate, etc. are the same as in Example 1 in both the following Examples and Comparative Examples.

Table 1 shows the paint formulations of Examples 1-2 and Comparative Examples 1-3. The results of each test are shown in Table-2.

31- (Note 4) Compatibility: After mixing each varnish except for the crosslinking agent, it was applied onto a glass plate using an applicator, and its transparency and texture were observed. The state after further drying at Vc of 140° C. for 30 minutes was observed. Next, a crosslinking agent is added and the same operation is performed. In any state, transparency tends to be high, and those with good smoothness are considered good.

(Note 5) The finished appearance of the paint film was evaluated based on the gloss and texture using the following criteria.

◎: Very good ○: Good @: Good condition ∆; Bad ×: Very poor (Note 6) Car wash scratch resistance: The test coated plate was attached to the ceiling of a passenger car and the car was washed 20 times in an automatic car wash. After that, the scratch condition of the test coated plate was evaluated according to the following criteria.

O: There are a lot of scratches 34- ○: There are a few scratches △: There are slight scratches ×: There are countless scratches (Note 7) Taber wear tester, worn ring C
8-10, the amount of weight loss after 500 rotations with a load of 1,000 g is displayed.

(Note 8) Waxing resistance: Automotive wax 5of
Apply a small amount of t99 Hanneri (Nitto Kagaku Co., Ltd. product) to a white flannel cloth, and use your index finger to spread the coated surface at a distance of 1051.
Rub vigorously back and forth. After that, wipe off the remaining wax on the painted surface with a new flannel cloth and observe the painted surface.

The degree of blurring, scratches, and coloring of the painted surface on the white flannel cloth was comprehensively evaluated using the following criteria.

◎: There are no glossy pockets on the painted surface, no scratches, and no discoloration of the flannel cloth.

35- ○: There is almost no gloss blurring on the painted surface, no scratches, and no discoloration of the flannel cloth.

＠: The painted surface is glossy, there are some scratches, and there is some discoloration from the paint on the ashinel cloth (practical limit).

△: The painted surface has a lot of dullness and scratches, and the flannel cloth is also slightly colored.

×: The paint surface is dull, the scratches are scratched, and the flannel is noticeably discolored.

(Note 9) Acid resistance: 10 sulfuric acid 0.5 CC was spotted on the coated surface and left at 20° C. and 75% RH for 48 hours, then washed with water and the coated surface was observed.

(Note 10) Apply gasoline wiping-resistant Nippon Seki Silver gasoline to gauze, and strongly tighten the length of 10 crn on the painted surface to 8
After rubbing back and forth, the painted surface was observed. A sample with almost no scratches or dullness on the painted surface was considered good.

(Note) Water resistance: Place the test piece in a constant temperature water bath at 40°C.
Soak for an hour. After removal, the paint film was rated as good if there were no abnormalities such as gloss, piquancy, or blistering.

(Note 12) Interlayer adhesion: Overbaked the top coated and baked test plate at 160°C for 30 minutes, and left it to cool at room temperature.
After some time, apply the same type of adjusted paint to 140℃ x 30
After baking for a minute, it was allowed to cool and a cross-cut to sellotape peeling test was performed, and those with no peeling were evaluated as good.

(Note 13) Painting workability: The adjusted diluted paint was air-sprayed and the sagging and scuffing properties were comprehensively evaluated.

(Note 14) Weather resistance: Q, UV (Q-Panel
The 60 degree specular reflectance (%) was measured using a 400-hour cycle of ultraviolet irradiation for 16 hours, temperature of 60°C, condensation for 8 hours, and temperature of 50°C using a tester (manufactured by Co., Ltd.).

Example 3 A main liquid of 60% acrylic resin varnish A 66.7 parts 60% oil-free polyester varnish A 50# 131ue 7040 10# was prepared in advance, and then the ratio of hydroxyl groups to isocyanate of the main liquid (OH/NCO Duranate 24A-100 (polyisocyanate manufactured by Mukasei Kogyo Co., Ltd.) was added so that the ratio (ratio) was 1, and then the viscosity was adjusted to 26 with a mixed solvent of Kijirol/butyl acetate/methyl isobutyl titone = 40/30/30. Diluted to sec, the CII:]-(2)
Spray the flexible material with air to a dry film thickness of 35μ, set it for 10 minutes, and then heat it at 80℃ x 1.
The test plate was baked for an hour and then left at 40°C for 24 hours to obtain a test coated plate.

As a result of the coating film performance test, 60° specular reflectance, 89°'l'
aber abrasion resistance, 91W, lead flower hardness, 3B, impact resistance, 38-, 50. Weather resistance, 82 and other performances listed in Table 2 were all good or ◎.

It also passed the test for low-temperature bending resistance (Note-15), which is an important function for flexible materials.

(Note-15) Low-temperature bending resistance: After placing the coated plate in a refrigerator at -30°C for 4 hours, it was immediately bent 180° with the coated side facing outward between iron rods with a diameter of 10 cm. After that, the coating film at the bent part is observed, and those with no cracks are passed, and those with cracks are rejected.

Examples 1 to 3 described above are examples of application of the present invention, and as a top coat (particularly, Examples 1 and 2 are for top coats on automobile bodies, and Example 3 is for top coats on flexible materials such as plastic bumpers). It has shown excellent properties in various tests, including scratch resistance and waxing resistance.

Comparative Example 1 uses oil-free polyester (B) and is composed only of acrylic resin (A) and crosslinking agent (C), and is poor in coating film appearance and glabella adhesion.

Comparative Example 2 is an example using oil-free polyester B. Since oil-free polyester B has poor compatibility, it has defects such as poor paint film appearance and lack of gloss, making it unsuitable as a top coat. has been omitted.

Comparative Example 3 is an example using an acrylic resin without using an e-caprolactone modified vinyl monomer, and has poor scratch resistance and waxing resistance.

From the above, it is clear that the top coating composition of the present invention has very excellent performance.

Patent applicant (140) Sekitoni Paint Co., Ltd. 40-

Claims (1)

[Scope of Claims] (A) ε-caprolactone modified vinyl monomer 5 represented by the following general formula % formula %)) where R represents H or CHm, and n is 0.5 to 5. ~
70% by weight and other radicata copolymerizable unsaturated monomers 95~
Hydroxyl value 20-20 obtained by copolymerizing with 30% by weight
(B) At least 30 moles of the acid component forming the polyester is a saturated alicyclic polybasic acid, and the total number of moles of the polybasic acid in the polyester raw material is equal to the total number of moles of the polyhydric alcohol. If the value divided by
0,8,100), (1,00°70), (1,00,
100); and (C) a top coating composition containing a crosslinking agent as a binder.