KR100484032B1 - Color-transparent 1-part paint composition - Google Patents

Abstract

 The present invention relates to a color-transparent one-part coating composition.

The coating composition of the present invention uses a polyol containing at least two or more hydroxyl groups in the molecule as a subject, an aminoalcohol modified isocyanate in which an isocyanate group containing at least one or more reactive silanes in the molecule as a curing agent is sealed as a blocking agent, It is composed of diluents, pigments and other components commonly used herein.

The coating composition according to the present invention configured as described above is excellent in adhesiveness with other materials to solve the adhesion failure during repainting and is excellent in hardness, scratch resistance and acid resistance of the cured coating film, and thus is suitable for automotive coating.

Description

Color-transparent, one-part coating composition

The present invention relates to a color-transparent one-part coating composition, and more particularly, it is excellent in adhesion to other materials and can solve the poor adhesion when repainting, and excellent hardness, scratch resistance and acid resistance of the cured coating film for automotive top coat To a suitable color-transparent one-part coating composition.

The top coat of automobiles is widely used in the form of a color-transparent coating in which a transparent paint is overlaid in a solid-color coating, which is a color-coating finish for producing color only. Such color coating compositions are disclosed in USP 4,220,679; 4,403,003; 4,147,569 and the like. Color-transparent paint is preferred because of its excellent appearance in terms of gloss, Distinctness of Image, and the like. This trend toward consumer appearance is leading to another demand for improvement of scratch resistance due to the rapid spread of auto washing machines. However, the scratches generated by the automatic washing machine are very different from those of the hand washing machine. It is due to the difference in magnitude of force applied, speed, direction and shape of contact material, hardness, friction coefficient, etc., and it adds to the difficulty of improvement.

In addition, the problems of acid rain, air pollution, etc., which are getting worse day by day, are increasing the damage of coatings, and thus, the development of coatings having excellent acid resistance is being encouraged. For example, the black coating film often rises to 70 ° C. or higher in the summer, and the area wetted by acid rain can cause very severe coating damage since the pH reaches 3 to 4.

As such an example, a conventional cured coating film using acrylic polyol-melamine has been widely used because of its excellent advantages in terms of appearance and price point. However, since it contains a large amount of the ether site which is easy to dissociate in acid rain, the acid resistance of a coating film is very weak and improvement is calculated | required.

As another example of the coating composition, two-component coating compositions prepared by using isocyanate as a curing agent in polyols such as polyester polyols, polyether polyols, polyurethane polyols, and acrylic polyols have been widely used industrially. However, the two-component coating composition may provide excellent gloss, image clarity, and acid resistance, but isocyanate is used as a curing agent, and thus, it is difficult to handle and sensitive to moisture.

As a means for solving this problem, a method of preparing a one-component coating composition by blocking an isocyanate group with a blocking agent has emerged. Examples of the blocking agent include phenols, alcohols, activated methylenes, mercaptans, imides, imines, pyrazoles, oximes, sulfites, and the like. The curing agent is achieved by dissociating the blocking agent again at high temperature to regenerate the isocyanate group. Done.

However, the blocked isocyanates lead to the disadvantages of lowering solubility and compatibility and deteriorating coating interlayer adhesion and coating appearance. In addition, since the undissociated isocyanate remains after curing, hardness and scratch resistance are inferior to those of the two-component coating composition. In particular, damage to the coating film due to acid rain is very serious due to insufficient acid resistance.

As an example to improve the acid resistance of the coating film, USP 4,499,151 is used for the production of acryl polyol. -Methacryloyloxypropyltrimethoxysilane, A method of copolymerizing a reactive silane-containing ethylenically unsaturated monomer such as -methacryloyloxypropylmethyldimethoxysilane and vinyltrimethoxysilane is disclosed.

However, the reactive silane-modified acrylic polyols can provide a cured coating film having excellent acid resistance, but have a disadvantage in that the appearance is poor, such as gloss, clearness, and image clarity, and poor crack resistance. In addition, high viscosity when copolymerizing ethylenically unsaturated monomers such as acrylic acid and methacrylic acid, which are commonly used for the purpose of providing interlayer adhesion and improving the dispersibility of pigments and additives when preparing ethylenically unsaturated copolymers in the art. There is a drawback that the application is not possible due to the rise or gelation phenomenon and the price is also very high.

After all, the object of the present invention is very good compatibility and solubility and excellent adhesion to other materials, so that the adhesion failure does not occur during re-coating, the high binding energy of the siloxane bond site formed in the coating film after curing, as well as hardness and scratch resistance The present invention provides a color-transparent one-part coating composition capable of forming this extremely excellent coating film.

The object of the present invention is achieved by using a polyol as the subject and using a silane containing blocked aminoalcohol modified isocyanate as the curing agent.

Specifically, the coating composition of the present invention is a conventional coating composition composed of a resin component, a diluent, a pigment, and other components, in which a polyol is used as a resin component and a silane-containing blocked amino alcohol-modified isocyanate as a curing agent. It has its features.

In particular, polyols containing at least two or more hydroxyl groups in the molecule as polyols (hereinafter component A) include silane containing encapsulated aminoalcohol-modified isocyanates containing at least one reactive silane in the molecule and isocyanate groups are blocked with a blocking agent. It is preferable to use amino alcohol-modified isocyanate (hereinafter referred to as component B).

The coating composition of the present invention configured as described above uses aminoalcohol-modified isocyanate as a base material to improve compatibility and solubility, and to improve adhesion to other materials through reactive silanes contained in the molecule, and also to form a coating film after curing. The high binding energy of the siloxane bonding portion formed therein can improve the hardness and scratch resistance as well as form a coating film having extremely excellent acid resistance.

The component A by this invention is demonstrated concretely.

Component A is a polyol component known in the art used to form urethane resins, and uses a polyol containing at least two hydroxyl groups in a molecule, and specific examples thereof include polyethers such as polyethylene glycol and polyflophylene glycol. Polyols; Polycarbonate polyols; Polyester polyols; Polyurethane polyols; Ethylenically unsaturated copolymer polyols such as acrylic polyols and vinyl polyols; Epoxy polyols; Celluloses; And polyhydric alcohols. Among them, ethylenically unsaturated copolymer polyols, which are easy to control coating film properties, are most suitable.

The ethylenically unsaturated copolymer polyols useful in the present invention do not limit the scope of the present invention, but the number average molecular weight is in the range of 1000 to 100,000 and the hydroxyl equivalent is in the range of 250 to 3000. Specific examples of hydroxyl group-containing ethylenically unsaturated monomers for forming such ethylenically unsaturated copolymers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth). ) Acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, ethylene oxide or propylene oxide addition type terminal hydroxyl group containing ethylene unsaturated monomers, etc. are mentioned. Can be. In addition, in the present invention, the hydroxyl group-containing ethylenically unsaturated monomer is more effectively used in copolymerization with a known ethylenically unsaturated monomer for the purpose of controlling viscosity, compatibility, solubility and hardness, gloss, glass transition temperature, etc. of the coating film. The ethylenically unsaturated copolymer polyol according to the present invention can be obtained by a polymerization method known in the art, and, for example, a solution polymerization method using a dilution solvent is most suitable and the number average molecular weight is in the range of 1000 to 100,000. It is desirable to control the initiator and the polymerization temperature so as to be.

The component B by this invention is demonstrated concretely.

Component B is first reacted with aminoalcohol (hereinafter referred to as component C) by adding at least one equivalent or more of a silane binder (hereinafter referred to as component D) containing a reactive silane, and then isocyanate (hereinafter referred to as isocyanate) in which an isocyanate group is partially blocked with a blocking agent. Prepared as a second reaction with residual active hydrogen).

In addition, component B may be prepared by first reacting component C with component E as a blocking agent, followed by secondary reaction with residual active hydrogen using at least one equivalent of component D, and may be reacted with a diluent solvent. . At this time, the reaction temperature is not particularly limited, but a normal temperature to 150 ℃ range is appropriate, the progress of the reaction can be confirmed by IR spectroscopy or wet analysis of the content of reactive groups, such as hydroxyl groups, amine groups, epoxy groups, isocyanate groups.

Component C is preferably an aminoalcohol containing at least one primary or secondary amine group and hydroxyl group in the molecule, and specific examples thereof include monoethanolamine, diethanolamine, mono-N-propylamine and di-N-propylamine. , Monoisopropanolamine, diisopropanolamine, monobutanolamine, dibutanolamine, 1-amino-6-hexanol, 1-amino-2-propanol, 1,1'-aminobis-2-propanol, 2-methylamino Ethanol, 2- (2-aminoethoxy) ethanol, 1,1'-aminobis-2-propanol, 2-methylaminoethanol, 2- (2-aminoethoxy) ethanol, 2- (methylamino) ethanol, 2-amino-1-butanol, 2- (cyclohexylamino) ethanol, 2- (phenylamino) ethanol, 4- (2-hydroxyethyl) morpholine, and the like.

Specific examples of component D include 2- (2,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxyhexyl) ) Ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- Epoxy group-containing reactive silanes such as glycidyloxypropyltriethoxysilane and 3-glycidyloxypropylethyldiethoxysilane; Isocyanate group containing reactive silanes, such as 3-isocyanatopropyl trimethoxysilane and 3-isocyanatopropyl triethoxysilane, etc. are mentioned.

Component E is a portion of a molecular isocyanate group blocked by a divalent or higher isocyanate compound (hereinafter referred to as component F) with a sequestering agent (hereinafter referred to as component G). At this time, the ratio of sequestration equivalent number is not particularly limited, but it is appropriate to control at least one or more isocyanate groups in the molecule of the component F, and more preferably about half of the isocyanate equivalent number is appropriate. If the ratio of blockade is too high, it is difficult to control the compatibility and solubility. On the contrary, if the ratio of blockage equivalent number is too low, the viscosity of the composition is high and it is difficult to control the degree of curing.

The reaction temperature for preparing component E is not particularly limited, but is suitable in the range from room temperature to 150 ° C, and the reaction rate can be controlled by quantifying the content of free isocyanate in the system through wet analysis, and diluent solvent and catalyst can be used if necessary. .

Specific examples of component F include 2,4-toluene diisocyanate, dimer of 2,4-toluene diisocyanate, O-naphthalene diisocyanate, diphenylmethane diisocyanate, triphenylmethanetriisocyanate, tris- (P-isocy Aromatic isocyanates such as anatophenyl) thiophosphate and polymethylene polyphenylisocyanate; Alicyclic or aliphatic isocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexyl diisocyanate and the like; There exists an addition type with polyhydric alcohols, such as a trimethylolpropane, or a biuret type, and it is more preferable to use alicyclic or aliphatic isocyanates which are excellent in yellowing resistance.

Specific examples of component G include phenols such as phenol, cresol, 0-isopropylphenol, thymol, P-tert-butylphenol and P-nitrophenol; Alcohols such as methanol, ethanol, butanol, ethylene glycol, butyl cellosolve, benzyl alcohol and cyclohexanol; Active methylenes such as dimethylmalonate, diethylmalonate and ethyl acetoacetate; Mercaptans such as butyl mercaptan, thiophenol, and dodecyl mercaptan; Imides such as succinimide and maleic acid imide; Amines such as diphenylamine, phenylnaphthylamine and arylene; Imidazoles such as 2-ethylimidazole; Urea such as urea, thiourea, ethylene urea; Imines, such as ethyleneimine; Hexamic acid esters such as arylmethylmethacryloyloxy hexamic acid ester; Oximes such as acetone oxime, 2-butanone oxime and cyclohexanone oxime; Pyrazoles such as 3,5-dimethylpyrazole; lactams such as ε-caprolactam and the like.

In the present invention, the ratio of the number of blocked isocyanate groups equivalents of component B to the number of hydroxyl groups equivalent of component A is in the range of 0.7 to 1.3. In the range below 0.7, there is a disadvantage in that storage capacity is low and the price is high, and in the range above 1.3, the degree of curing is low and acid resistance is poor.

The coating composition according to the present invention is characterized in that it is used in one-part form by adding the auxiliary resin, the diluent solvent and the other components used in the paint to the components A and B, and may further add a pigment as necessary.

Auxiliary resins include malamine resins, polyester resins, silicone modified polyester resins, silicone resins, vinyl resins, and the like. As the dilution solvent, solvents such as xylene, toluene, butyl acetate, ethyl cellosolve, Hansol, butanol, methyl ethyl ketone, and methyl isobutyl ketone may be used. Other components also include dehumidifying agents such as trimethyl orthoacetate, trimethyl orthobutylate, oxazolines, and monoisocyanates; Reaction catalysts such as organometallic salts, tertiary amines and amine salts; Thickeners; Rheology modifiers; Wetting agents; Popping agent; Leveling agent; UV absorbers; There are known additives such as antioxidants.

The coating composition according to the present invention is also applicable to a solid-color coating composition. In order to improve the appearance, glossiness, etc. of the coating film, it is also possible to apply a so-called "2 coat 1 bake" method in which the coating composition of the present invention is coated in the wet state and then heat cured. At this time, the heat curing condition is suitable for about 15 to 60 minutes at 120 to 180 ° C. If the heating temperature is low, the curing time is long and uncured products are generated. If the heating temperature is high, the energy consumption is high and yellowing film is generated. Problems arise.

Hereinafter, the production examples and the comparative production examples of the components A, B, and E will be described.

[Production of Component A]

Preparation Example A-1

In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 100 parts by weight of butyl acetate, 100 parts by weight of toluene, and 200 parts by weight of xylene were added and maintained at reflux of the solvent under stirring, followed by hydroxyl-containing ethylenically unsaturated monomer. 300 parts by weight of phosphorus 2-hydroxyethyl methacrylate, 270 parts by weight of ethylene unsaturated monomers, 50 parts by weight of methyl methacrylate, 250 parts by weight of N-butyl methacrylate, 100 parts by weight of butyl acrylate, meta 30 parts by weight of acrilic acid and a mixture of 70 parts by weight of 1,1'-azobis (1-cyclohexanecarbonitrile), which is a radical initiator, are added dropwise uniformly over 2 hours, and then maintained for 2 hours. The mixture was cooled to room temperature and then adjusted to a solid content of 70% using xylene to obtain an ethylenically unsaturated copolymer polyol solution component A-1 having a Gardner viscosity of Y-Z.

Preparation Example A-2

In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 100 parts by weight of butyl acetate, 100 parts by weight of toluene, and 200 parts by weight of xylene were added and maintained at reflux of the solvent under stirring, followed by hydroxyl-containing ethylenically unsaturated monomer. Phosphorus 4-hydroxybutyl acrylate 150 parts by weight, 2-hydroxypropyl acrylate 50 parts by weight, methyl methacrylate 200 parts by weight of ethylenically unsaturated monomer, 250 parts by weight of butyl acrylate, 4-hydroxybutyl acrylate 200 parts by weight, 50 parts by weight of ethylhexyl acrylate, 100 parts by weight of isobornyl acrylate, 200 parts by weight of cyclohexyl methacrylate and 50 parts by weight of a radical initiator tert-butylperacetate were added dropwise and uniformly over 3 hours. Keep it for 2 hours. The mixture was cooled to room temperature and then adjusted to 70% solids using xylene to obtain an ethylenically unsaturated copolymer polyol solution component A-2 having a Gardner viscosity of V-W.

Preparation Example A-3

100 parts by weight of butyl acetate, 100 parts by weight of methyl isobutyl ketone, 200 parts by weight of xylene and 1,3-bis [3- (2,3) in a 4-necked flask equipped with a stirrer, a cooler and a thermometer. Ethoxypropoxy) propyl] tetramethyldisiloxane 260 parts by weight of diethanolamine 440 while paying attention to exotherm at room temperature with a mixture of 500 parts by weight of 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane The weight part was added dropwise over 3 hours, and the temperature was raised to 60 ° C. over 2 hours. Then, IR spectroscopy and wet analysis terminate the reaction at the time when the epoxy group disappears and cool to room temperature. Xylene was adjusted to 70% solids to obtain an epoxy polyol solution component A-3 having a Gardner viscosity of S.

Preparation Example A-4

110 parts by weight of neotentyl glycol, 130 parts by weight of 1,6-hexanediol, 200 parts by weight of trimethylolpropane, 510 parts by weight of dimethylisophthalate, azelaic acid 120 in a four-necked flask equipped with a stirrer, a cooler, a condenser and a thermometer. Add a weight part and heat it under nitrogen injection to melt the contents gradually. The temperature is raised step by step to remove the condensed water continuously and finally maintain the 220 ℃ state. Through wet analysis, the reaction is terminated at the acid value of 4.5 and cooled to room temperature. Dilution with xylene to adjust the solids content to 70% by weight yielded a polyester polyol solution component A-4 having a polystyrene relative comparison number average molecular weight of 2300 and a hydroxyl value of 130.

Comparative Production Example A-5

In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 100 parts by weight of butyl acetate, 100 parts by weight of toluene, and 200 parts by weight of xylene were added and heated and stirred to keep the solvent at reflux. Then, the hydroxyl group-containing ethylenically unsaturated monomer was added. 300 parts by weight of phosphorus 2-hydroxyethyl methacrylate, 70 parts by weight of methyl methacrylate which is an ethylenically unsaturated monomer, 100 parts by weight of styrene, 200 parts by weight of N-butyl acrylate, and 30 parts by weight of acrylic acid, and 300 parts by weight of methacryloyloxyethylpropyltrimethoxysilane, which is a silane group-containing ethylenically unsaturated monomer, and tert-butylperacetate, which is a radical initiator, were added dropwise at a rate of 5 parts by weight per minute. The reaction was terminated by gelation at about 40 minutes after the dropping started.

Comparative Production Example A-6

In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 100 parts by weight of butyl acetate, 100 parts by weight of toluene and 200 parts by weight of xylene were added and heated and stirred to keep the solvent at reflux, and then the hydroxyl group-containing ethylenically unsaturated monomer. 300 parts by weight of phosphorus 2-hydroxyethyl methacrylate, 100 parts by weight of methyl methacrylate which is an ethylenically unsaturated monomer, 100 parts by weight of styrene, 300 parts by weight of N-butylacryloyloxyethylpropyl trimethoxysilane, A mixture of 70 parts by weight of 1,1'-bisazo (1-cyclohexanecarbonitrile), which is a radical initiator, is added dropwise and uniformly over 3 hours and then maintained for 2 hours. After cooling to room temperature, xylene was adjusted to 70% solids to obtain component A-5 having a Gardner viscosity of Z.

[Production of Component E]

Preparation Example E-1

Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, a mixture of 150 parts by weight of dried butyl acetate, a dilute solvent, and 665 parts by weight of isophorone diisocyanate, component F, 200 parts by weight of dried butyl acetate and component G 295 parts by weight of the mixture of 3,5-dimethylpyrazole is added dropwise over 1 hour. After standing at room temperature for 1 day, the temperature was raised to 60 ° C., and the reaction was terminated when the free isocyanate content was 9.6% by weight through wet analysis to cool down to room temperature. Drying butyl acetate adjusted the solids content to 70% by weight to obtain component E-1.

Preparation Example E-2

Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 100 parts by weight of dried butyl acetate, a diluent solvent, and 670 parts by weight of 1,3,5-tris (6-isocyanatohexyl) -Burette, component F A mixture of 300 parts by weight of dried butyl acetate, a diluent solvent, and 460 parts by weight of aryl methacryloxyhydroxyxamic acid ester, component G, was added dropwise over 1 hour, and the temperature was raised to 60 ° C. to give 4.1% by weight of free isocyanate through wet analysis. At the time of%, the reaction is terminated and cooled to room temperature. The dried content of butyl acetate was adjusted to 70% by weight to obtain component E-2.

Preparation Example E-3

In a four-necked flask equipped with a stirrer, a cooler and a thermometer, 200 parts by weight of dried butyl acetate as a diluting solvent and 505 parts by weight of tris (6-isocyanatohexyl) -isocyanurate as component F were added. 85 parts by weight of a 2-butanone oxime mixture is added dropwise over 1 hour, and then heated to 60 ° C. 2 parts by weight of dibutyl tin dilaurate as a reaction catalyst was added to the reaction mixture, and the reaction was terminated when the free isocyanate content was 10.6% by weight through wet analysis. Component E-3 was obtained by adjusting the solid content to 70% by weight with dried butyl acetate.

[Production of Component B]

Preparation Example B-1

Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 80 parts by weight of 6-aminohexanol as component C was added, and 200 parts by weight of 3-isocyanatopropyltrimethoxysilane as component D was added dropwise over 1 hour, followed by 70 ° C. Will raise the temperature. 2 parts by weight of dibutyltin dilaurate, a reaction catalyst, was added to the reaction mixture, and the reaction was terminated by the IR spectroscopy and wet analysis. After completion of the first reaction, 460 parts by weight of component E-1 was added. Spectroscopy and wet analysis terminate the reaction at the point where the isocyanate groups disappear and allow it to cool to room temperature. The component B-1 was obtained by adjusting so that solid content might be 70 weight% with the dried butyl acetate.

Preparation Example B-2

Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, add 80 parts by weight of 6-aminohexane, component C, and add 460 parts by weight of component E-1 over 1 hour, and then raise the temperature to 70 ° C. 2 parts by weight of dibutyl dilaurate as a reaction catalyst was added to the reaction mixture, and the reaction was terminated at the point where the isocyanate disappeared through IR spectroscopy and wet analysis. As a secondary reaction, 200 parts by weight of 3-isocyanatopropyltrimethoxysilane, which is component D, was added dropwise over 1 hour, and the reaction was terminated at room temperature after the isocyanate group disappeared through IR spectroscopy and wet analysis. The component B-2 was obtained by adjusting so that solid content may be 70 weight% with the dried butyl acetate.

Preparation Example B-3

Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 235 parts by weight of 3-glycidyloxypropyltrimethoxysilane as component D was added to a mixture of 100 parts by weight of butyl acetate, a diluent solvent, and 105 parts by weight of diethanolamine, component C. It heats up at 140 degreeC. After adding 3 parts by weight of triethylamine, a reaction catalyst, and maintaining the reaction, the first reaction was terminated when the epoxy group disappeared through IR spectroscopy and wet analysis. As a secondary reaction, 1370 parts by weight of component E-1 was added dropwise over 1 hour, followed by a holding reaction to terminate the reaction when the isocyanate group disappeared through IR spectroscopy and wet analysis to cool down to room temperature. The component B-3 was obtained by adjusting so that solid content might be 70 weight% with the dried butyl acetate.

Preparation Example B-4

In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 55 parts by weight of 2- (2-aminoethoxy) ethanol as component C was placed and 150 parts by weight of 3-isocyanatopropyltrimethoxysilane as component D over 1 hour. After dropping, the temperature is maintained at 60 ° C. 5 parts by weight of zinc diethylhexanoate, a reaction catalyst, was added to the reaction mixture, and the reaction was terminated by IR spectroscopy and wet analysis. 790 parts by weight of component E-2 was added thereto, followed by maintenance reaction. After the isocyanate group disappeared through IR spectroscopy and wet analysis, the secondary reaction was terminated and cooled to room temperature. The component B-4 was obtained by adjusting so that solid content might be 70 weight% with the dried butyl acetate.

Preparation Example B-5

Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, a mixture of 90 parts by weight of 2- (ethylamino) ethanol as component C and 80 parts by weight of 2,2-iminobis-N-butanol was added and 3-isocyane as component D was added. 375 parts by weight of Itopropyltriethoxysilane was added dropwise over 1 hour, and the temperature was maintained at 60 ° C. IR spectroscopy and wet analysis terminate the first reaction at the point where the isocyanate groups disappear. 915 parts by weight of component E-1 was added thereto, followed by maintenance reaction. After completion of the secondary reaction at the time when the isocyanate group disappeared through IR spectroscopy and wet analysis, the mixture was cooled to room temperature. The component B-5 was obtained by adjusting so that solid content may be 70 weight% with the dried butyl acetate.

Preparation Example B-6

Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 300 parts by weight of 2-component (cyclohexylamino) hexanol, component C, were added dropwise a mixture of 230 parts by weight of component E-1 and 210 parts by weight of component E-3 over 1 hour. After that, keep the temperature at 60 ° C. IR spectroscopy and wet analysis terminate the first reaction at the point where the isocyanate groups disappear. 100 parts by weight of 3-isocyanatopropyltrimethoxysilane, which is component D, was added to the reaction mixture, and the mixture was cooled and cooled to room temperature after terminating the secondary reaction at the time when the isocyanate group disappeared through IR spectroscopy and wet analysis. Ingredient B-6 was obtained by adjusting the solid content to 70% by weight with dried butyl acetate.

Preparation Example B-7

Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, a mixture of 20 parts by weight of 2-aminoethanol, component C, and 55 parts by weight of 2- (2-aminoethoxy) ethanol was added, and 3-isocyanatopropyl tree, which was component D. 300 parts by weight of methoxysilane is added dropwise over 1 hour, and the temperature is raised to 60 ° C. to maintain the reaction. IR spectroscopy and wet analysis terminate the first reaction at the point where the isocyanate groups disappear. 460 parts by weight of component E-1 is added dropwise over 1 hour, followed by a maintenance reaction. Then, the IR spectroscopy and wet analysis terminate the secondary reaction when the isocyanate group disappears and cool to room temperature. The component B-7 was obtained by adjusting so that solid content might be 70 weight% with the dried butyl acetate.

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples.

Example 1

Component A-1 480 parts by weight, curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt) 50 parts by weight, coating film smoothing agent (disparon LC-951, Kusumoto Japan) 5 parts by weight, ultraviolet absorber (tinuvin 328, Swiss Ciba-Geigy Co., Ltd.) 20 parts by weight of a high speed dissolver was stirred at a speed of 2000 rpm for 30 minutes to disperse well, and 20 parts by weight of a viscoelastic modifier (Chicksarol 289, Enel Co., Ltd.) was added thereto, followed by stirring for 15 minutes. . Then, add 480 parts by weight of component B-3 and 30 parts by weight of melamine resin (Cymel 303, Monsanto, USA), and further stirred for 15 minutes, and adjust the viscosity to 60 seconds with pod cup NO.4 using xylene. -1 was obtained.

Example 2

300 parts by weight of component A-2, 30 parts by weight of trimethylolpropane as component A, 50 parts by weight of a curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt), 5 parts by weight of a coating film smoothing agent (polybutyl acrylate), ultraviolet absorber 20 parts by weight of (2,4-dihydroxybenzophenone) and 10 parts by weight of a light stabilizer (Tinuvin 328, Shiba-Geigy Co., Ltd.) were dispersed using a high speed dissolver at a speed of 2000 rpm for 30 minutes and then dispersed well. 20 parts by weight of a regulator (Chicksarol 289, Enel, USA) was added and stirred for 15 minutes to disperse. Next, 670 parts by weight of component B-1 was added thereto, followed by further stirring for 15 minutes, and the viscosity was adjusted to 55 seconds with pod cup NO.4 using xylene to obtain a desired coating composition 1-2.

Example 3

185 parts by weight of component A-2, 25 parts by weight of component A-3, 60 parts by weight of a curing catalyst (N- (4-methoxybenzyl-0-N, N-dimethylanilinium P-dodecylbenzenesulfonate), coating film 10 parts by weight of a leveling agent (polybutyl acrylate), 20 parts by weight of an ultraviolet absorber (Tinuvin 328, Sibagai Co., Ltd.), 50 parts by weight of a dehumidifying agent (trimethyl ortho acetate) at a speed of 2000 rpm using a high speed dissolba After stirring for 30 minutes to disperse well, add 20 parts by weight of a viscoelastic modifier (Chicksarol 289, Enel Co., Ltd.), and further stirred for 15 minutes, and adjust the viscosity to 60 seconds with a pod cup NO.4 using xylene. 1-3 was obtained.

Example 4

Component A-4 210 parts by weight, curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt) 50 parts by weight, coating film leveling agent (polybutyl acrylate) 10 parts by weight, ultraviolet absorber (tinuvin 328, Swiss Ciba-Geigy Co., Ltd.) 20 parts by weight of a high speed dissolva was stirred for 30 minutes at a speed of 2000 rpm, followed by good dispersion. Then, 20 parts by weight of a viscoelastic modifier (Chicksarol 289, Enel, USA) was added and stirred for 15 minutes to disperse. Next, 250 parts by weight of component B-6 and 340 parts by weight of component B-7 were added thereto, and the mixture was further stirred for 15 minutes, and the viscosity was adjusted to 60 seconds with pod cup NO.4 using xylene to obtain a desired coating composition 1-4.

Example 5

Component A-1 470 parts by weight, curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt) 50 parts by weight, coating film smoothing agent (polybutyl acrylate) 10 parts by weight, ultraviolet absorber (tinuvin 389, Swiss Ciba-Geigy Co., Ltd.) 20 parts by weight, 10 parts by weight of a light stabilizer (Tinuvin 123, Shiba-Geigy Co., Ltd.) was dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissolba, and then a viscoelastic modifier (Chicksarol 289, Enel, USA) 20 Part by weight was added and stirred for 15 minutes to disperse. Then add 250 parts by weight of component B-6, 510 parts by weight of component B-6, and 30 parts by weight of melamine resin (Cymel 222, Cytec, USA) for 15 minutes and stir for 60 seconds using xylene with Pod Cup NO.4. The viscosity was adjusted to give the desired coating composition 1-5.

Comparative Example 6

Component A-1 520 parts by weight, curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt) 20 parts by weight, coating film leveling agent (polybutyl acrylate) 20 parts by weight, ultraviolet absorber (tinuvin 389, Shiba GIGA Co., Ltd.) 30 parts by weight, light stabilizer (Tinuvin 123, Siba, Ltd., Switzerland) 20 parts by weight using a high speed dissolva, stirred at 2000 rpm for 30 minutes to disperse well, and then viscoelastic modifier (Chicksarol 289, Enel Corporation, USA) 20 Part by weight was added and stirred again for 15 minutes to disperse. Isophorodiisocyanate, in which all isocyanate groups are blocked with 2-butanone oxime, is dissolved in dried butyl acetate, and 480 parts by weight of a solution having a solid content of 70% by weight is added and stirred for 15 minutes. The viscosity was adjusted to 55 seconds to obtain Comparative Paint Composition 1-6.

Comparative Example 7

Component A-1 870 parts by weight, curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt) 50 parts by weight, coating film leveling agent (polybutyl acrylate, BASF, Germany) 10 parts by weight, ultraviolet absorber (tinuvin 389, Switzerland 20 parts by weight of Ciba-Geigy Co., Ltd. and 10 parts by weight of a light stabilizer (Tinuvin 123, Swiss Ciba-Geigy Co., Ltd.) were dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissolba, and then a viscoelastic imparting agent (Chick Satro 289, 20 parts by weight of Enel US) was added and stirred for 15 minutes to disperse. Next, 90 parts by weight of melamine resin (Cymel 303, Cytec Co., Ltd.) was added thereto, followed by further stirring for 15 minutes, and the viscosity was adjusted to 55 seconds with pod cup NO.4 using xylene to obtain Comparative Coating Composition 1-7.

Comparative Example 8

Component A-6 520 parts by weight, curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt) 50 parts by weight, coating film leveling agent (polybutyl acrylate) 10 parts by weight, ultraviolet absorber (tinuvin 389, Swiss Ciba-Geigy Co., Ltd.) 20 parts by weight, 10 parts by weight of light stabilizer (Tinuvin 123, Shiba-Geigy Co., Ltd.) was dispersed using a high speed dissolba at 30 rpm for 30 minutes to disperse well, and then a viscoelasticity imparting agent (Chicksarol 289, Enel, USA) 20 parts by weight was added and stirred again for 15 minutes to disperse. Next, 480 parts by weight of a solution of 2-butanone oxime-blocked isophorodiisocyanate dissolved in dried butyl acetate and a solid content of 70% by weight was added and stirred for 15 minutes, followed by 60 seconds in a pod cup NO.4 using xylene. The viscosity was adjusted so as to obtain Comparative Paint Composition 1-8.

Comparative Example 9

Component A-6 870 parts by weight, curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt) 50 parts by weight, coating film leveling agent (polybutyl acrylate, BASF Germany) 10 parts by weight, ultraviolet absorber (tinuvin 389, Switzerland 20 parts by weight of Ciba-Geigy Co., Ltd. and 10 parts by weight of a light stabilizer (Tinuvin 123, Swiss Ciba-Geigy Co., Ltd.) were dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissolba, and then a viscoelastic imparting agent (Chick Satro 289, 20 parts by weight of Enel US) was added and stirred again for 15 minutes to disperse. Next, 90 parts by weight of melamine resin (Cymer 303, Cytec Co., Ltd.) was dissolved in dried butyl acetate, a solution having a solid content of 70% by weight was added and stirred for 15 minutes, followed by 55 seconds using xylene in a pod cup NO.4. The viscosity was adjusted to obtain Comparative Paint Composition 1-9.

Comparative Example 9

1000 parts by weight of component A-6, 50 parts by weight of a curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt), 10 parts by weight of a coating film leveling agent (polybutylacrylate, BASF, Germany), UV absorber (Tinuvin 389, Switzerland) 20 parts by weight of Ciba-Geigy Co., Ltd. and 10 parts by weight of a light stabilizer (Tinuvin 123, Swiss Ciba-Geigy Co., Ltd.) were dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissolba, and then a viscoelastic imparting agent (Chick Satro 289, 20 parts by weight of Enel US) was added and stirred for 15 minutes to disperse. Next, the viscosity was adjusted to 55 seconds using xylene with Pod Cup NO.4 to obtain Comparative Coating Composition 1-10.

[Comparison of Application Properties of Paints]

After the electrodeposition and the intermediate coating finish, the horizontal × vertical = 200mm × 200mm sized zinc sheet using a bell-type automatic coating machine was color-coated to 20㎛ thickness, and left for 5 minutes at 70% relative humidity × room temperature. The coating composition of Preparation Examples and Comparative Preparation Examples was adjusted to 35 seconds with Pod Cup NO.4 using xylene, followed by two subsequent straight coatings with a thickness of 40 μm, then left for 10 minutes and then at 145 ° C. Curing in a controlled oven for 25 minutes to prepare a coating material test specimen.

Its physical property test results are shown in Table 1.

In Table 2, c means that a crack has occurred.

Appearance was visually judged and was marked as (circle) = excellent, (triangle | delta) = good, * = inadequate, and * x = poor.

Repaintability is the test of "CROSS CUT TAPE ADHESION" as described in ASTM D3359 after the coating film property test specimen is left at 150 ° C for 1 hour and then repainted the color and transparent coatings in the same manner and then cured at 145 ° C for 25 minutes. It evaluated and described by the method and showed (circle) = 100/100, (triangle | delta) = 95/100 or more, x = 90/100 or more, and less than xx = 90/100.

Wear resistance was evaluated and indicated according to the test method using the "TABER ABRASER" group by the method described in ASTM D 4060.

Pencil hardness was evaluated according to the ASTM D 3363 test method and displayed.

Acid resistance was dropped by dropping 10% sulfuric acid solution on the coating film with a dropper and left in an oven at 70 ℃ for 5 minutes. ○ = No damage area △ = Only marks left X = Fine marks XX = Fine marks severe.

The yellowing resistance was measured by measuring the E value of the coating material test specimen by COLORY-METER, and then left at 150 ° C. for 1 hour, and the E value was measured again to indicate a change value ΔE.

The weather resistance was expressed by comparing the degree of gloss loss according to the ASTM D 523 test method in parallel with the American Arizona EMMAQUQ test and the Florida exposure test.

As can be seen from the above test results, the color-transparent one-component coating composition according to the present invention uses amino alcohol-modified isocyanate as a base material, so that compatibility and solubility are very good, and at the same time with other materials through the reactive silane contained in the molecule. It can be seen that it is possible to provide a coating composition without the problem of poor adhesion when repainting is possible to excellent adhesion. In addition, it can be clearly seen that the high binding energy of the siloxane bonding portion formed in the coating film after curing can form a coating film having extremely high hardness and scratch resistance as well as excellent acid resistance.

Claims (8)

A color-transparent, one-component coating composition based on polyols and containing a reactive silane containing blocked amino alcohol-modified isocyanate as a curing agent. The method of claim 1, wherein the polyol is at least one selected from polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, ethylenically unsaturated copolymer polyols, celluloses, and polyhydric alcohols. Color-transparent, one-part coating composition. The method of claim 1, wherein the reactive silane-containing blocked aminoalcohol-modified isocyanate is reacted with at least one equivalent or more of the silane-binding agent containing a reactive silane to aminoalcohol, and then the remaining isocyanate is used as a blocking agent. A color-transparent one-part coating composition obtained by secondary reaction with active hydrogen. The method of claim 1, wherein the reactive silane-containing blocked aminoalcohol-modified isocyanate is residual by using at least one equivalent of a silane-containing silane binder after the first reaction of the isocyanate group partially blocked by an isocyanate group with a blocking agent to aminoalcohol. A color-transparent one-part coating composition obtained by secondary reaction with active hydrogen. The color-transparent, one-part coating composition according to claim 3 or 4, wherein the amino alcohol contains at least one amine group and hydroxyl group in the molecule. The color-transparent one-part coating composition according to claim 3 or 4, wherein the silane binder containing the reactive silane is a silane binder containing an epoxy group or a silane binder containing an isocyanate group. The color-transparent, one-part coating composition according to claim 3 or 4, wherein the isocyanate in which the isocyanate group is partially blocked by the blocking agent is obtained by reacting at least divalent isocyanate with the blocking agent. 8. The color-transparent, one-part coating composition according to claim 7, wherein the isocyanate in which the isocyanate group is partially blocked by the blocking agent is obtained by reacting at least one isocyanate group in the molecule.